CN109879989B - Polyvinyl phosphoric acid and preparation method thereof - Google Patents
Polyvinyl phosphoric acid and preparation method thereof Download PDFInfo
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Abstract
The invention provides a preparation method of polyvinyl phosphoric acid, which is characterized by comprising the following steps: step 1: adding PVC, phosphate and a solvent into a reaction kettle, heating to 60-100 ℃ and reacting for 24-72 h; step 2: filtering the reaction liquid obtained in the step 1, and washing the obtained filter cake for 3-5 times by using ethanol and distilled water in sequence to obtain phosphate resin; and step 3: adding the phosphate resin obtained in the step 2 into a reaction kettle, then adding concentrated hydrochloric acid, heating to 60-100 ℃, and carrying out hydrolysis reaction for 24-72 h; and 4, step 4: and (3) filtering the reaction liquid obtained in the step (3), washing the obtained filter cake for 3-5 times by using distilled water, and then drying the washed filter cake to obtain the polyvinyl phosphoric acid. The phosphoric acid resin obtained by the invention has uniform particle size of 100-300 mu m and high functional group content (up to 10 mmol/g).
Description
Technical Field
The invention relates to a phosphoric acid resin and a preparation method thereof, belonging to the field of functional polymers.
Background
The acidic resin is high molecular solid acid which takes a cross-linked polymer as a framework, is connected with an acidic functional group and can react with metal ions from a solution containing the metal ions to form an ionic bond. Then, under proper elution condition, the metal ions on the resin can be released. The base material of the high molecular solid acid may be crosslinked polystyrene, crosslinked polyphenol, crosslinked polyacrylic acid, or the like. The polymer is prepared by suspension polymerization of conventional monomers, and has the characteristics of mature preparation process, easy functionalization, high mechanical strength and good chemical stability.
The prior phosphoric acid resin has the defect of low content of functional groups, thereby limiting the application of the resin; and the technical problems of complex process, difficult treatment after reaction and the like exist in the resin preparation process.
Disclosure of Invention
The invention aims to provide a phosphoric acid resin with high functional group content and a preparation method thereof.
The technical principle of the invention is as follows: the reaction equation schematic diagram of the preparation process of the crosslinked polyvinyl phosphate is shown in fig. 1, and firstly, on the basis of crosslinked polyvinyl chloride resin beads, chlorine element reacts with phosphate ester, phosphate ester groups are introduced onto a polymer chain, and then the phosphate ester groups are hydrolyzed into phosphate groups through hydrolysis reaction. The obtained phosphoric acid resin not only has higher functional group content (more than 5mmol/g and up to 10mmol/g), but also can be used as ion exchange resin; and the formed phosphoric acid resin has good stability and is convenient for regeneration and utilization.
The technical scheme adopted by the invention is as follows:
the preparation method of polyvinyl phosphoric acid is characterized by comprising the following steps:
step 1: adding PVC, phosphate and a solvent into a reaction kettle, heating to 60-100 ℃ and reacting for 24-72 h; the PVC: phosphate ester: the mass ratio of the solvent is 1: 1-10: 10-50 parts of; the PVC is cross-linked polyvinyl chloride microspheres; the phosphate is trimethyl phosphite, triethyl phosphite or a mixture of trimethyl phosphite and triethyl phosphite; the solvent is one or more than two of 2-methyltetrahydrofuran, petroleum ether and N, N-dimethylformamide;
step 2: filtering the reaction liquid obtained in the step 1, and sequentially washing the obtained filter cake for 3-5 times by using ethanol and water respectively to obtain phosphate resin;
and step 3: adding the phosphate resin obtained in the step 2 into a reaction kettle, then adding concentrated hydrochloric acid, heating to 60-100 ℃, and carrying out hydrolysis reaction for 24-72 h; the usage amount of the phosphate resin and the concentrated hydrochloric acid is calculated according to the mass ratio that: concentrated hydrochloric acid is 1: 3-10;
and 4, step 4: and (3) filtering the reaction liquid obtained in the step (3), washing the obtained filter cake for 3-5 times by using water, and then drying the washed filter cake to obtain the polyvinyl phosphoric acid.
Preferably, the reaction time in step 1 is 48 to 72 hours, and more preferably 72 hours.
Preferably, the reaction temperature in step 1 is 100 ℃.
Preferably, the PVC: phosphate ester: the mass ratio of the solvent is 1: 5-10: 30-40, more preferably 1:10: 30.
preferably, the phosphate in step 1 is trimethyl phosphite, and the solvent is N, N-dimethylformamide.
Preferably, the phosphate in step 1 is triethyl phosphite, and the solvent is 2-methyltetrahydrofuran.
Preferably, the temperature in step 3 is 100 ℃, and the hydrolysis reaction is carried out for 72 hours.
Preferably, in step 3, the ratio of phosphate ester resin to concentrated hydrochloric acid is calculated according to the mass ratio of phosphate ester resin: concentrated hydrochloric acid is 1: 5-10.
Preferably, the phosphate ester resin and the concentrated hydrochloric acid in the step 3 are used in a mass ratio of phosphate ester resin: concentrated hydrochloric acid is 1:5 or 1: 7.
preferably, the drying temperature in the step 4 is 105 ℃ and the pressure is 0.1 MPa.
The invention also provides the polyvinyl phosphoric acid prepared by the preparation method.
Furthermore, the functional group content of the polyvinyl phosphoric acid is 5-10mmol/g, and the particle size is 100-300 μm.
Furthermore, the content of functional groups of the polyvinyl phosphoric acid is 9-10 mmol/g.
Compared with the prior art, the invention has the beneficial effects that:
according to the preparation method of the functionalized polyethylene, disclosed by the invention, because the preparation process is based on crosslinked polyvinyl chloride resin beads, chlorine and phosphate ester react to introduce phosphate ester groups onto a polymer chain, and the phosphate ester groups are hydrolyzed into phosphate groups through hydrolysis reaction. The method is simple and clear, the material cost is low, the process preparation is simple, and the adsorbent can be repeatedly used, so that the method has a good application prospect.
Furthermore, the phosphoric acid resin obtained by the preparation method of the phosphoric acid resin has uniform particle size of 100-300 μm and high functional group content (up to 10 mmol/g).
The resin prepared by the method has good ion exchange performance for various metal ions, high exchange rate, high functional group content and easy regeneration and reuse.
Drawings
FIG. 1 is a schematic view showing the reaction equation of the process for preparing polyvinyl phosphoric acid according to the present invention.
FIG. 2 is a scanning electron micrograph of a phosphoric acid resin obtained in example 1 of the present invention.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The method for measuring the content of the functional group of the obtained phosphoric acid resin (refer to the method for measuring the content of the functional group in polypropylene, Huangwenqiang, ion exchange and adsorption resin [ M ]. Shanghai: Shanghai science and technology education Press, 1992).
The raw materials and equipment used in the examples of the present invention are commercially available, unless otherwise specified.
The methods in the following examples are conventional in the art unless otherwise specified.
Example 1
A preparation method of polyvinyl phosphoric acid comprises the following specific steps:
(1) adding 10g of PVC into a reaction kettle, sequentially adding 50g of phosphate and 100g of solvent, and heating to 80 ℃ to react for 24 hours to obtain reaction liquid;
the amount of PVC, solvent and phosphate used in the above reaction is calculated according to the mass ratio, namely PVC: phosphate ester: calculating the ratio of the solvent to be 1:5: 10;
the phosphate is trimethyl phosphite;
the solvent is 2-methyltetrahydrofuran;
the PVC is cross-linked polyvinyl chloride microspheres with the particle size of 100-300 mu m, and is produced by Shanghai Qingyuan resin Co., Ltd;
(2) filtering the reaction liquid obtained in the step (1), and sequentially and respectively washing the obtained filter cake for 3 times by using ethanol and distilled water to obtain a filter cake, namely the phosphate resin;
(3) adding the phosphate ester resin obtained in the step (2) into a reaction kettle, adding 95mL of concentrated hydrochloric acid with the concentration of 36%, and heating to 80 ℃ to perform hydrolysis reaction for 24 hours to obtain a reaction solution; the amount of the phosphate resin and the concentrated hydrochloric acid used in the reaction is calculated according to the mass ratio, namely the phosphate resin: calculating the ratio of concentrated hydrochloric acid to hydrochloric acid of 1: 3;
(4) and (3) filtering the reaction liquid obtained in the step (3), washing the obtained filter cake for 3 times by using distilled water, and drying the washed filter cake for 8 hours at the temperature of 105 ℃ and the pressure of 0.1Mpa to obtain the cross-linked polyvinyl phosphoric acid.
The polyvinylphosphoric acid obtained in example 1 was scanned by an S-3400N Scanning Electron Microscope (SEM) manufactured by Hitachi-New Nake, and the obtained SEM image is shown in FIG. 2. As can be seen from FIG. 2, the particle size is uniform and is between 100 and 300 μm.
The polyvinyl phosphoric acid thus obtained was measured to have a functional group content of 5.1 mmol/g.
Example 2
A preparation method of polyvinyl phosphoric acid comprises the following specific steps:
(1) adding 10g of PVC into a reaction kettle, sequentially adding 60g of phosphate and 200g of solvent, and heating to 100 ℃ to react for 24 hours to obtain reaction liquid;
the amount of PVC, solvent and phosphate used in the above reaction is calculated according to the mass ratio, namely PVC: phosphate ester: calculating the ratio of the solvent to be 1:6: 20;
the phosphate is trimethyl phosphite;
the solvent is petroleum ether;
the PVC is cross-linked polyvinyl chloride microspheres with the particle size of 100-300 mu m, and is produced by Shanghai Qingyuan resin Co., Ltd;
(2) filtering the reaction liquid obtained in the step (1), and sequentially and respectively washing the obtained filter cake for 3 times by using ethanol and distilled water to obtain a filter cake, namely the phosphate resin;
(3) adding the phosphate ester resin obtained in the step (2) into a reaction kettle, then adding 100mL of concentrated hydrochloric acid with the concentration of 36%, and then heating to 80 ℃ for hydrolysis reaction for 24 hours to obtain a reaction solution;
the amount of the phosphate resin and the concentrated hydrochloric acid used in the reaction is calculated according to the mass ratio, namely the phosphate resin: calculating the ratio of concentrated hydrochloric acid to hydrochloric acid of 1: 3;
(4) filtering the reaction liquid obtained in the step (3), washing the obtained filter cake for 3 times by using distilled water, and drying the washed filter cake for 8 hours at the temperature of 105 ℃ and the pressure of 0.1Mpa to obtain the polyvinyl phosphoric acid.
The particle size of the polyvinyl phosphoric acid obtained by the method is determined to be uniform and is between 100-300 mu m.
The polyvinyl phosphoric acid thus obtained was measured to have a functional group content of 5.8 mmol/g.
Example 3
A preparation method of polyvinyl phosphoric acid comprises the following specific steps:
(1) adding 10g of PVC into a reaction kettle, sequentially adding 60g of phosphate and 300g of solvent, and heating to 80 ℃ to react for 36 hours to obtain reaction liquid;
the amount of PVC, solvent and phosphate used in the above reaction is calculated according to the mass ratio, namely PVC: phosphate ester: calculating the ratio of the solvent to be 1:6: 30;
the phosphate is trimethyl phosphite;
the solvent is 2-methyltetrahydrofuran;
the PVC is cross-linked polyvinyl chloride microspheres with the particle size of 100-300 mu m, and is produced by Shanghai Qingyuan resin Co., Ltd;
(2) filtering the reaction liquid obtained in the step (1), and washing the obtained filter cake for 3 times by using ethanol and distilled water respectively in sequence to obtain a filter cake, namely the phosphate resin;
(3) adding the phosphate ester resin obtained in the step (2) into a reaction kettle, then adding 100mL of concentrated hydrochloric acid with the concentration of 36%, and then heating to 80 ℃ for hydrolysis reaction for 24 hours to obtain a reaction solution;
the amount of the phosphate resin and the concentrated hydrochloric acid used in the reaction is calculated according to the mass ratio, namely the phosphate resin: calculating the ratio of concentrated hydrochloric acid to hydrochloric acid of 1: 3;
(4) and (3) filtering the reaction liquid obtained in the step (3), washing the obtained filter cake for 3 times by using distilled water, and drying the washed filter cake for 8 hours at the temperature of 105 ℃ and the pressure of 0.1Mpa to obtain the polyvinyl phosphoric acid.
The particle size of the polyvinyl phosphoric acid obtained by the method is determined to be uniform and is between 100-300 mu m.
The polyvinyl phosphoric acid thus obtained was measured to have a functional group content of 6.3 mmol/g.
Example 4
A preparation method of polyvinyl phosphoric acid comprises the following specific steps:
(1) adding 10g of PVC into a reaction kettle, sequentially adding 80g of phosphate and 300g of solvent, and heating to 100 ℃ to react for 36 hours to obtain a reaction solution;
the amount of PVC, solvent and phosphate used in the above reaction is calculated according to the mass ratio, namely PVC: phosphate ester: calculating the ratio of the solvent to be 1:8: 30;
the phosphate is trimethyl phosphite;
the solvent is N, N-dimethylformamide;
the particle size of the PVC cross-linked polyvinyl chloride microspheres is 100-300 mu m, and the PVC cross-linked polyvinyl chloride microspheres are produced by Shanghai Qingyuan resin Co., Ltd;
(2) filtering the reaction liquid obtained in the step (1), and sequentially and respectively washing the obtained filter cake for 3 times by using ethanol and distilled water to obtain a filter cake, namely the phosphate resin;
(3) adding the phosphate ester resin obtained in the step (2) into a reaction kettle, then adding 100mL of concentrated hydrochloric acid with the concentration of 36%, and then heating to 80 ℃ for hydrolysis reaction for 24 hours to obtain a reaction solution;
the amount of the phosphate resin and the concentrated hydrochloric acid used in the reaction is calculated according to the mass ratio, namely the phosphate resin: calculating the ratio of concentrated hydrochloric acid to hydrochloric acid of 1: 3;
(4) and (3) filtering the reaction liquid obtained in the step (3), washing the obtained filter cake for 3 times by using distilled water, and drying the washed filter cake for 8 hours at the temperature of 105 ℃ and the pressure of 0.1Mpa to obtain the polyvinyl phosphoric acid.
The particle size of the polyvinyl phosphoric acid obtained by the method is determined to be uniform and is between 100-300 mu m.
The content of the functional group in the polyvinyl phosphoric acid thus obtained was measured to be 8.0 mmol/g.
Example 5
A preparation method of polyvinyl phosphoric acid comprises the following specific steps:
(1) adding 10g of PVC into a reaction kettle, sequentially adding 80g of phosphate and 300g of solvent, and heating to 80 ℃ to react for 48 hours to obtain reaction liquid;
the amount of PVC, solvent and phosphate used in the above reaction is calculated according to the mass ratio, namely PVC: phosphate ester: calculating the ratio of the solvent to be 1:8: 30;
the phosphate is triethyl phosphite;
the solvent is 2-methyltetrahydrofuran;
the PVC is cross-linked polyvinyl chloride microspheres with the particle size of 100-300 mu m, and is produced by Shanghai Qingyuan resin Co., Ltd;
(2) filtering the reaction liquid obtained in the step (1), and sequentially and respectively washing the obtained filter cake for 5 times by using ethanol and distilled water to obtain a filter cake, namely the phosphate resin;
(3) adding the phosphate ester resin obtained in the step (2) into a reaction kettle, then adding concentrated hydrochloric acid with the concentration of 100 being 36%, and then heating to 100 ℃ for hydrolysis reaction for 24 hours to obtain reaction liquid;
the amount of the phosphate resin and the concentrated hydrochloric acid used in the reaction is calculated according to the mass ratio, namely the phosphate resin: calculating the ratio of concentrated hydrochloric acid to hydrochloric acid of 1: 3;
(4) and (3) filtering the reaction liquid obtained in the step (3), washing the obtained filter cake for 3 times by using distilled water, and drying the washed filter cake for 8 hours at the temperature of 105 ℃ and the pressure of 0.1Mpa to obtain the polyvinyl phosphoric acid.
The particle size of the polyvinyl phosphoric acid obtained by the method is determined to be uniform and is between 100-300 mu m.
The polyvinyl phosphoric acid thus obtained was measured to have a functional group content of 7.6 mmol/g.
Example 6
A preparation method of polyvinyl phosphoric acid comprises the following specific steps:
(1) adding 10g of PVC into a reaction kettle, then sequentially adding 100g of phosphate and 300g of solvent, and then heating to 85 ℃ to react for 60 hours to obtain reaction liquid;
the amount of PVC, solvent and phosphate used in the above reaction is calculated according to the mass ratio, namely PVC: phosphate ester: calculating the ratio of the solvent to be 1:10: 30;
the phosphate is triethyl phosphite;
the solvent is petroleum ether;
the PVC is cross-linked polyvinyl chloride microspheres with the particle size of 100-300 mu m, and is produced by Shanghai Qingyuan resin Co., Ltd;
(2) filtering the reaction liquid obtained in the step (1), and sequentially and respectively washing the obtained filter cake for 3 times by using ethanol and distilled water to obtain a filter cake, namely the phosphate resin;
(3) adding the phosphate ester resin obtained in the step (2) into a reaction kettle, then adding 150mL of concentrated hydrochloric acid with the concentration of 36%, and then heating to 100 ℃ for hydrolysis reaction for 48 hours to obtain a reaction solution;
the amount of the phosphate resin and the concentrated hydrochloric acid used in the reaction is calculated according to the mass ratio, namely the phosphate resin: calculating the ratio of concentrated hydrochloric acid to hydrochloric acid of 1: 5;
(4) and (3) filtering the reaction liquid obtained in the step (3), washing the obtained filter cake for 3 times by using distilled water, and drying the washed filter cake for 8 hours at the temperature of 105 ℃ and the pressure of 0.1Mpa to obtain the polyvinyl phosphoric acid.
The particle size of the polyvinyl phosphoric acid obtained by the method is determined to be uniform and is between 100-300 mu m.
The polyvinyl phosphoric acid thus obtained was measured to have a functional group content of 8.6 mmol/g.
Example 7
A preparation method of polyvinyl phosphoric acid comprises the following specific steps:
(1) adding 10g of PVC into a reaction kettle, sequentially adding 100g of phosphate and 400g of solvent, and heating to 90 ℃ to react for 72 hours to obtain a reaction solution;
the amount of PVC, solvent and phosphate used in the above reaction is calculated according to the mass ratio, namely PVC: phosphate ester: calculating the ratio of the solvent to be 1:10: 40;
the phosphate is triethyl phosphite;
the solvent is N, N-dimethylformamide;
the PVC is cross-linked polyvinyl chloride microspheres with the particle size of 100-300 mu m, and is produced by Shanghai Qingyuan resin Co., Ltd;
(2) filtering the reaction liquid obtained in the step (1), and washing the obtained filter cake for 4 times by using ethanol and distilled water respectively in sequence to obtain a filter cake, namely the phosphate resin;
(3) adding the phosphate ester resin obtained in the step (2) into a reaction kettle, then adding 350mL of concentrated hydrochloric acid with the concentration of 36%, and then heating to 100 ℃ for hydrolysis reaction for 48 hours to obtain a reaction solution;
the amount of the phosphate resin and the concentrated hydrochloric acid used in the reaction is calculated according to the mass ratio, namely the phosphate resin: calculating the ratio of concentrated hydrochloric acid to concentrated hydrochloric acid of 1: 10;
(4) and (3) filtering the reaction liquid obtained in the step (3), washing the obtained filter cake for 3 times by using distilled water, and drying the washed filter cake for 8 hours at the temperature of 105 ℃ and the pressure of 0.1Mpa to obtain the polyvinyl phosphoric acid.
The particle size of the polyvinyl phosphoric acid obtained by the method is determined to be uniform and is between 100-300 mu m.
The polyvinyl phosphoric acid thus obtained was measured to have a functional group content of 9.7 mmol/g.
Example 8
A preparation method of polyvinyl phosphoric acid comprises the following specific steps:
(1) adding 10g of PVC into a reaction kettle, sequentially adding 100g of phosphate and 500g of solvent, and heating to 70 ℃ to react for 48 hours to obtain a reaction solution;
the amount of PVC, solvent and phosphate used in the above reaction is calculated according to the mass ratio, namely PVC: phosphate ester: calculating the ratio of the solvent to be 1:10: 50;
the phosphate is triethyl phosphite;
the solvent is N, N-dimethylformamide;
the PVC is cross-linked polyvinyl chloride microspheres with the particle size of 100-300 mu m, and is produced by Shanghai Qingyuan resin Co., Ltd;
(2) filtering the reaction liquid obtained in the step (1), and sequentially and respectively washing the obtained filter cake for 5 times by using ethanol and distilled water to obtain a filter cake, namely the phosphate resin;
(3) adding the phosphate ester resin obtained in the step (2) into a reaction kettle, then adding 350mL of concentrated hydrochloric acid with the concentration of 36%, and then heating to 90 ℃ to perform hydrolysis reaction for 72 hours to obtain a reaction solution;
the amount of the phosphate resin and the concentrated hydrochloric acid used in the reaction is calculated according to the mass ratio, namely the phosphate resin: calculating the ratio of concentrated hydrochloric acid to concentrated hydrochloric acid of 1: 10;
(4) and (3) filtering the reaction liquid obtained in the step (3), washing the obtained filter cake for 3 times by using distilled water, and drying the washed filter cake for 8 hours at the temperature of 105 ℃ and the pressure of 0.1Mpa to obtain the polyvinyl phosphoric acid.
The particle size of the polyvinyl phosphoric acid obtained by the method is determined to be uniform and is between 100-300 mu m.
The polyvinyl phosphoric acid thus obtained was measured to have a functional group content of 10.2 mmol/g.
Example 9
A preparation method of polyvinyl phosphoric acid comprises the following specific steps:
(1) adding 10g of PVC into a reaction kettle, sequentially adding 80g of phosphate and 500g of solvent, and heating to 70 ℃ to react for 72 hours to obtain reaction liquid;
the amount of PVC, solvent and phosphate used in the above reaction is calculated according to the mass ratio, namely PVC: phosphate ester: calculating the ratio of the solvent to be 1:8: 50;
the phosphate is trimethyl phosphite;
the solvent is 2-methyltetrahydrofuran;
the PVC is cross-linked polyvinyl chloride microspheres with the particle size of 100-300 mu m, and is produced by Shanghai Qingyuan resin Co., Ltd;
(2) filtering the reaction liquid obtained in the step (1), and sequentially and respectively washing the obtained filter cake for 3 times by using ethanol and distilled water to obtain a filter cake, namely the phosphate resin;
(3) adding the phosphate ester resin obtained in the step (2) into a reaction kettle, then adding 270mL of concentrated hydrochloric acid with the concentration of 36%, and then heating to 120 ℃ for hydrolysis reaction for 72 hours to obtain a reaction solution;
the amount of the phosphate resin and the concentrated hydrochloric acid used in the reaction is calculated according to the mass ratio, namely the phosphate resin: calculating the ratio of concentrated hydrochloric acid to concentrated hydrochloric acid of 1: 8;
(4) and (3) filtering the reaction liquid obtained in the step (3), washing the obtained filter cake for 3 times by using distilled water, and drying the washed filter cake for 8 hours at the temperature of 105 ℃ and the pressure of 0.1Mpa to obtain the polyvinyl phosphoric acid.
The particle size of the polyvinyl phosphoric acid obtained by the method is determined to be uniform and is between 100-300 mu m.
The polyvinyl phosphoric acid thus obtained was measured to have a functional group content of 7.8 mmol/g.
Example 10
A preparation method of polyvinyl phosphoric acid comprises the following specific steps:
(1) adding 10g of PVC into a reaction kettle, sequentially adding 90g of phosphate and 400g of solvent, and heating to 60 ℃ to react for 72 hours to obtain a reaction solution;
the amount of PVC, solvent and phosphate used in the above reaction is calculated according to the mass ratio, namely PVC: phosphate ester: calculating the ratio of the solvent to be 1:9: 40;
the phosphate is trimethyl phosphite;
the solvent is 2-methyltetrahydrofuran;
the PVC is cross-linked polyvinyl chloride microspheres with the particle size of 100-300 mu m, and is produced by Shanghai Qingyuan resin Co., Ltd;
(2) filtering the reaction liquid obtained in the step (1), and sequentially and respectively washing the obtained filter cake for 3 times by using ethanol and distilled water to obtain a filter cake, namely the phosphate resin;
(3) adding the phosphate ester resin obtained in the step (2) into a reaction kettle, then adding 160mL of concentrated hydrochloric acid with the concentration of 36%, and then heating to 120 ℃ for hydrolysis reaction for 72 hours to obtain a reaction solution;
the amount of the phosphate resin and the concentrated hydrochloric acid used in the reaction is calculated according to the mass ratio, namely the phosphate resin: calculating the ratio of concentrated hydrochloric acid to hydrochloric acid of 1: 5;
(4) and (3) filtering the reaction liquid obtained in the step (3), washing the obtained filter cake for 3 times by using distilled water, and drying the washed filter cake for 8 hours at the temperature of 105 ℃ and the pressure of 0.1Mpa to obtain the polyvinyl phosphoric acid.
The particle size of the polyvinyl phosphoric acid obtained by the method is determined to be uniform and is between 100-300 mu m.
The polyvinyl phosphoric acid thus obtained was measured to have a functional group content of 7.1 mmol/g.
Example 11
A preparation method of polyvinyl phosphoric acid comprises the following specific steps:
(1) adding 10g of PVC into a reaction kettle, sequentially adding 70g of phosphate and 300g of solvent, and heating to 100 ℃ to react for 60 hours to obtain a reaction solution;
the amount of PVC, solvent and phosphate used in the above reaction is calculated according to the mass ratio, namely PVC: phosphate ester: calculating the ratio of the solvent to be 1:7: 30;
the phosphate is trimethyl phosphite;
the solvent is 2-methyltetrahydrofuran;
the PVC is cross-linked polyvinyl chloride microspheres with the particle size of 100-300 mu m, and is produced by Shanghai Qingyuan resin Co., Ltd;
(2) filtering the reaction liquid obtained in the step (1), and sequentially and respectively washing the obtained filter cake for 4 times by using ethanol and distilled water to obtain a filter cake, namely the phosphate resin;
(3) adding the phosphate ester resin obtained in the step (2) into a reaction kettle, then adding 220mL of concentrated hydrochloric acid with the concentration of 36%, and then heating to 120 ℃ for hydrolysis reaction for 72 hours to obtain a reaction solution;
the amount of the phosphate resin and the concentrated hydrochloric acid used in the reaction is calculated according to the mass ratio, namely the phosphate resin: calculating the ratio of concentrated hydrochloric acid to concentrated hydrochloric acid of 1: 7;
(4) and (3) filtering the reaction liquid obtained in the step (3), washing the obtained filter cake with distilled water, and drying the washed filter cake for 8 hours at the temperature of 105 ℃ and the pressure of 0.1Mpa to obtain the polyvinyl phosphoric acid.
The particle size of the polyvinyl phosphoric acid obtained by the method is determined to be uniform and is between 100-300 mu m.
The polyvinyl phosphoric acid thus obtained was measured to have a functional group content of 6.8 mmol/g.
In conclusion, the preparation method of the phosphoric acid resin has the advantages of simple and clear steps, low material cost, simple process preparation, reusable adsorbent and good application prospect. Meanwhile, the diameter of the polyvinyl phosphate beads obtained is uniform and is 100-300 μm. Furthermore, the obtained polyvinyl phosphoric acid has high functional group content, and the functional group content is 5-10mmol/g, preferably 9-10mmol/g
The above description is only a basic description and preferred embodiments of the present invention, and any equivalent changes made according to the technical solution of the present invention should fall within the protection scope of the present invention.
Claims (9)
1. The preparation method of polyvinyl phosphoric acid is characterized by comprising the following steps:
step 1: adding PVC, phosphate and a solvent into a reaction kettle, heating to 60-100 ℃ and reacting for 24-72 h; the PVC: phosphate ester: the mass ratio of the solvent is 1: 1-10: 10-50 parts of; the PVC is cross-linked polyvinyl chloride microspheres; the phosphate is trimethyl phosphite, triethyl phosphite or a mixture of trimethyl phosphite and triethyl phosphite; the solvent is one or more than two of 2-methyltetrahydrofuran, petroleum ether and N, N-dimethylformamide;
step 2: filtering the reaction liquid obtained in the step 1, and sequentially washing the obtained filter cake for 3-5 times by using ethanol and water respectively to obtain phosphate resin;
and step 3: adding the phosphate resin obtained in the step 2 into a reaction kettle, then adding concentrated hydrochloric acid, heating to 60-100 ℃, and carrying out hydrolysis reaction for 24-72 h; the usage amount of the phosphate resin and the concentrated hydrochloric acid is calculated according to the mass ratio that: concentrated hydrochloric acid is 1: 3-10;
and 4, step 4: and (3) filtering the reaction liquid obtained in the step (3), washing the obtained filter cake for 3-5 times by using water, and then drying the washed filter cake to obtain the polyvinyl phosphoric acid.
2. The method for preparing polyvinylphosphoric acid according to claim 1, wherein the reaction time in step 1 is from 48 to 72 hours; the reaction temperature in step 1 is 100 ℃.
3. The method of preparing polyvinyl phosphoric acid according to claim 1, wherein the PVC in step 1: phosphate ester: the mass ratio of the solvent is 1: 5-10: 30-40.
4. The method of claim 1, wherein the phosphate in step 1 is trimethyl phosphite and the solvent is N, N-dimethylformamide, or the phosphate in step 1 is triethyl phosphite and the solvent is 2-methyltetrahydrofuran.
5. The method for preparing polyvinyl phosphoric acid according to claim 1, wherein the temperature in step 3 is 100 ℃, and the hydrolysis reaction is carried out for 72 hours, and in step 3, the mass ratio of the phosphate ester resin to the concentrated hydrochloric acid is calculated according to the usage amount of the phosphate ester resin: concentrated hydrochloric acid is 1: 5-10.
6. The method of claim 1, wherein the drying temperature in step 4 is 105 ℃ and the pressure is 0.1 MPa.
7. The polyvinyl phosphoric acid produced by the method for producing polyvinyl phosphoric acid according to any one of claims 1 to 6.
8. The polyvinyl phosphoric acid as claimed in claim 7, wherein the polyvinyl phosphoric acid has a functional group content of 5 to 10mmol/g and a particle size of 100 μm and 300. mu.m.
9. The polyvinyl phosphoric acid according to claim 7, wherein the polyvinyl phosphoric acid has a functional group content of 9 to 10 mmol/g.
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