CN116813076A - Preparation method of modified polyurethane filler - Google Patents
Preparation method of modified polyurethane filler Download PDFInfo
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- CN116813076A CN116813076A CN202310927136.6A CN202310927136A CN116813076A CN 116813076 A CN116813076 A CN 116813076A CN 202310927136 A CN202310927136 A CN 202310927136A CN 116813076 A CN116813076 A CN 116813076A
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- 239000000945 filler Substances 0.000 title claims abstract description 116
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 53
- 239000004814 polyurethane Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000000243 solution Substances 0.000 claims abstract description 54
- 238000012986 modification Methods 0.000 claims abstract description 38
- 230000004048 modification Effects 0.000 claims abstract description 38
- 239000011259 mixed solution Substances 0.000 claims abstract description 27
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 15
- 150000002978 peroxides Chemical class 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000012266 salt solution Substances 0.000 claims abstract description 7
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 10
- 239000011790 ferrous sulphate Substances 0.000 claims description 10
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- 229960002089 ferrous chloride Drugs 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 6
- 244000005700 microbiome Species 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 9
- 239000002351 wastewater Substances 0.000 abstract description 7
- 238000002715 modification method Methods 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000005273 aeration Methods 0.000 description 4
- -1 iron ions Chemical class 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
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- 239000000463 material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
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- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
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Landscapes
- Biological Treatment Of Waste Water (AREA)
Abstract
The invention relates to the technical field of polymer carrier modification, in particular to a preparation method of modified polyurethane filler. The method comprises the steps of mixing a peroxide solution and a ferrous salt solution, and adjusting the pH value to obtain a mixed solution; and immersing the polyurethane filler into the mixed solution for modification to finally obtain the modified polyurethane filler. The novel polyurethane filler obtained by the modification method has greatly improved biocompatibility, has larger specific surface area compared with the traditional polyurethane filler, has promotion effect on adsorbing and growing microorganisms on the surface of the filler to form a biological film, and can improve the treatment efficiency of the polyurethane filler on wastewater in a biological film method.
Description
Technical Field
The invention relates to the technical field of polymer carrier modification, in particular to a preparation method of modified polyurethane filler.
Background
The biomembrane method is a water treatment technology for sewage biological treatment by utilizing microorganisms attached to a carrier material, and the carrier material has the main function of providing a microenvironment for the survival of the microorganisms, so that the stress resistance of the microorganisms to various pollutants is greatly improved. Compared with other similar materials, the polyurethane filler has large specific surface area, and can realize good separation from water while maintaining enough thallus quantity. However, the immobilization of microorganisms is achieved only by physical adsorption, which leads to easy shedding of microorganism cells, and thus, modification treatment is required to increase the surface roughness and the surface biocompatibility.
Modifications of the filler currently include bulk modification and surface modification. Bulk modification of polyurethane fillers is mostly achieved by adding nanomaterials such as nano SiO to the filler 2 Although the affinity and physical and chemical stability of the filler to microorganisms can be improved, the filler is expensive and not easy to obtain, and has certain limitation in popularization. The mechanical modification in the surface modification is suitable for the filler with a metal coating, and the surface roughening method needs to process the filler in a mould, and is not suitable for polyurethane filler; the low-temperature plasma modification and high-energy radiation modification have small environmental pollution and short processing period, but the application conditions are severe, and the method is not suitable for popularization. The prior widely applied liquid phase chemical oxidation method and surface grafting method are mainly adopted. The latter is mainly grafted with sodium alginate and gelatin protein. After chemical oxidation, the surface of the material becomes rough, and ion coverage or surface grafting is added after oxidation in many researches to strengthen the modification effect. For example, potassium permanganate oxidation-iron ion overlay modification and potassium permanganate oxidation-gelatin protein graft modification are used, and studies have shown that gelatin protein graft modification is performed after oxidation compared with Fe 3+ The effect of coverage modification is slightly better, but Fe 3+ The modification treatment cost is lower.
Therefore, how to provide a modification method with light pollution, convenience and lower cost, which modifies the biocompatibility of polyurethane filler, can accelerate the film formation of microorganisms on the surface of polyurethane filler and strengthen the stability of the biomembrane and the filler, is a technical problem to be solved in the field.
Disclosure of Invention
The invention aims to provide a preparation method of modified polyurethane filler, which is used for modifying the biological affinity of the polyurethane filler, so that the film hanging of microorganisms on the surface of the polyurethane filler is quickened, the stability of a biological film and the filler is enhanced, and the problems that the biological film of the polyurethane filler has long film hanging time, the biological film is easy to fall off and the like are solved.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of modified polyurethane filler, which comprises the following steps:
(1) Mixing a peroxide solution and a ferrous salt solution, and adjusting the pH value to obtain a mixed solution;
(2) Immersing polyurethane filler into the mixed solution for modification to obtain modified polyurethane filler.
Preferably, in the step (1), the pH is adjusted by using sodium hydroxide solution, hydrochloric acid solution or sulfuric acid solution; the concentration of the sodium hydroxide solution is 0.1-0.5 mol/L; the concentration of the hydrochloric acid solution is 0.1-0.5 mol/L; the concentration of the sulfuric acid solution is 0.1-0.5 mol/L; the pH value of the mixed solution is less than or equal to 3.
Preferably, the concentration of the peroxide in the mixed solution in the step (1) is 0.1-10 mmol/L.
Preferably, the concentration of the ferrous salt in the mixed solution in the step (1) is 0.1-10 mmol/L.
Preferably, the peroxide solution in step (1) comprises a hydrogen peroxide solution, a peracetic acid solution or a sodium persulfate solution.
Preferably, the ferrous salt solution in the step (1) comprises one or more of ferrous sulfate solution and ferrous chloride solution.
Preferably, the temperature of the modification in the step (2) is 15-25 ℃ and the time is 1-4 h.
Preferably, after the modification in the step (2) is finished, drying is carried out to obtain modified polyurethane filler; the drying temperature is 100-120 ℃ and the drying time is 40-60 min.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a modification method for modifying polyurethane filler by utilizing hydroxyl radicals and iron ions generated in the advanced oxidation reaction process by taking ferrous ions as a catalyst and peroxide as an oxidant, which is applicable to aquatic organism treatment.
According to the method for modifying the surface structure of the polyurethane filler, the hydroxyl radical generated in the advanced oxidation reaction process is utilized to oxidize the surface of the filler so as to improve the surface roughness of the filler and increase the specific surface area of the filler; as the surfaces of the cell membranes of the microorganisms are negatively charged, the surface of the filler is modified by utilizing iron ions generated by the reaction to change the potential of the surface of the filler, so that the biological affinity of the filler is improved, and the enrichment and the fixation of microorganisms are facilitated.
Compared with the traditional polyurethane filler, the polyurethane filler prepared by the modification method has larger specific surface area, has promotion effect on the adsorption and growth of microorganisms on the surface of the filler to form a biomembrane, can be applied to biomembrane method, and can improve the treatment efficiency of wastewater.
Drawings
FIG. 1 is a graph showing the change of the biofilm loading with time before and after modification of the polyurethane filler of example 1 of the present invention;
FIG. 2 is a graph showing the ammonia nitrogen removal rate with time before and after modification of the polyurethane filler in example 1 of the present invention;
FIG. 3 is a graph showing the COD removal rate with time before and after modification of the polyurethane filler in example 1 of the present invention.
Detailed Description
The invention provides a preparation method of modified polyurethane filler, which comprises the following steps:
(1) Mixing a peroxide solution and a ferrous salt solution, and adjusting the pH value to obtain a mixed solution;
(2) Immersing polyurethane filler into the mixed solution for modification to obtain modified polyurethane filler.
In the present invention, the step (1) uses sodium hydroxide solution, hydrochloric acid solution or sulfuric acid solution to adjust the pH, preferably uses hydrochloric acid solution or sulfuric acid solution to adjust the pH;
the concentration of the sodium hydroxide solution is 0.1 to 0.5mol/L, preferably 0.2 to 0.4mol/L, and more preferably 0.25 to 0.35mol/L; the concentration of the hydrochloric acid solution is 0.1 to 0.5mol/L, preferably 0.2 to 0.4mol/L, and more preferably 0.25 to 0.35mol/L; the concentration of the sulfuric acid solution is 0.1 to 0.5mol/L, preferably 0.2 to 0.4mol/L, and more preferably 0.25 to 0.35mol/L;
the pH of the mixed solution is not more than 3, preferably not more than 2.5, more preferably not more than 2, still more preferably not more than 1.5.
In the present invention, the concentration of the peroxide in the mixed solution of the step (1) is 0.1 to 10mmol/L, preferably 1 to 8mmol/L, more preferably 2 to 6mmol/L, still more preferably 4 to 5mmol/L.
In the present invention, the concentration of the divalent iron salt in the mixed solution of the step (1) is 0.1 to 10mmol/L, preferably 1 to 8mmol/L, more preferably 2 to 6mmol/L, still more preferably 4 to 5mmol/L.
In the present invention, the peroxide solution in the mixed solution of step (1) has the same concentration as the divalent iron ion.
In the present invention, the peroxide solution in the step (1) comprises a hydrogen peroxide solution, a peracetic acid solution or a sodium persulfate solution, preferably a hydrogen peroxide solution or a peracetic acid solution, and more preferably a peracetic acid solution.
In the present invention, the ferrous salt solution in the step (1) contains one or more of a ferrous sulfate solution and a ferrous chloride solution, preferably a ferrous sulfate solution.
In the present invention, the temperature of the modification in the step (2) is 15 to 25 ℃, preferably 16 to 24 ℃, more preferably 18 to 22 ℃, still more preferably 20 ℃; the time is 1 to 4 hours, preferably 1.5 to 3.5 hours, more preferably 2 to 3 hours, still more preferably 2.5 hours.
In the invention, after the modification in the step (2) is finished, drying is carried out to obtain modified polyurethane filler; the drying temperature is 100-120 ℃, preferably 102-115 ℃, and further preferably 105-110 ℃; the time is 40 to 60 minutes, preferably 45 to 55 ℃, more preferably 48 to 53 ℃, still more preferably 50 ℃.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Mixing the peracetic acid solution and the ferrous sulfate solution, and adopting H with the concentration of 0.1mol/L 2 SO 4 The pH value of the mixed solution is regulated to 3, the concentration of the peroxyacetic acid in the mixed solution is 1.0mmol/L, and the concentration of the ferrous sulfate is 1.0mmol/L; completely immersing polyurethane filler in the mixed solution at 20 ℃ for 2 hours for modification; and after modification, drying the filler at a high temperature of 105 ℃ for 60min to obtain the modified polyurethane filler.
Example 2
Mixing the peracetic acid solution and the ferrous sulfate solution, and adopting H with the concentration of 0.1mol/L 2 SO 4 The pH value of the mixed solution is regulated to 3, the concentration of the peroxyacetic acid in the mixed solution is 0.1mmol/L, and the concentration of the ferrous sulfate is 0.1mmol/L; completely immersing polyurethane filler in the mixed solution at 20 ℃ for 1h for modification; and after modification, drying the filler at a high temperature of 105 ℃ for 60min to obtain the modified polyurethane filler.
Example 3
Mixing the peracetic acid solution and the ferrous sulfate solution, and adopting H with the concentration of 0.1mol/L 2 SO 4 The pH value of the mixed solution is regulated to 3, the concentration of the peroxyacetic acid in the mixed solution is 10mmol/L, and the concentration of the ferrous sulfate is 10mmol/L; completely immersing polyurethane filler in the mixed solution at 20 ℃ for 4 hours for modification; and after modification, drying the filler at a high temperature of 105 ℃ for 60min to obtain the modified polyurethane filler.
Test case
The experimental method comprises the following steps:
glucose is used as a carbon source, ammonium bicarbonate is used as a nitrogen source for manual water distribution, COD (chemical oxygen demand) of water distribution is 340mg/L, and ammonia nitrogen concentration is 22mg/L. The modified filler prepared in example 1 and the unmodified filler were charged respectively in two identical reactors (effective volume: 1L) at a filler/solution filling ratio (filler volume/solution volume) of 5%.
Film hanging stage: and respectively inoculating an equivalent amount of aeration Chi Wuni of the sewage treatment plant, uniformly mixing the aeration, standing, discharging sludge after 24 hours, and finishing the inoculation at the moment. Adding water again, performing aeration reaction, controlling dissolved oxygen to be 6-8 mg/L, changing water every 24h, and ending the film forming stage after 3 days.
Sampling: and (3) performing a performance test of the filler treated wastewater after film formation, controlling the dissolved oxygen to be 6-8 mg/L, and performing operation period to be 24 hours, wherein aeration is performed for 23 hours, standing is performed for 50 minutes, and water is changed for 10 minutes. And detecting COD and ammonia nitrogen values of water discharged from the two reactors when water is changed at the end of each running period, and respectively taking out the modified filler and the unmodified filler for testing the amount of the biological membrane.
The analysis method comprises the following steps:
(1) Biofilm assay method: putting the taken out film-forming filler (the self weight W1 and g of the filler) into a weighing bottle wrapped by lining tinfoil, drying the film-forming filler in an oven at 105 ℃ for 60min, weighing the film-forming filler (W2 and g) after cooling, taking out the filler, putting the film-forming filler into a NaOH solution at 1mol/L, heating the film-forming filler in a water bath for 1h at 70 ℃, then carrying out ultrasonic treatment for 1h at 40Hz, washing the film-forming filler for several times until the falling biological film is washed off, putting the filler into the weighing bottle for drying, cooling and weighing the film-forming filler (W3 and g), and calculating (W2-W3) by 1000/W1, namely the dry weight (mg/g) of the biological film on the unit mass filler.
(2) The COD removal rate test method comprises the following steps: and measuring COD of the inlet water and the outlet water by adopting a potassium dichromate method, and dividing the COD removal amount by the COD of the inlet water to obtain the COD removal rate.
(3) The ammonia nitrogen removal rate testing method comprises the following steps: and measuring ammonia nitrogen in and out of the water by adopting a Nahner reagent photometry, and dividing the ammonia nitrogen removal amount by the ammonia nitrogen in the water to obtain the ammonia nitrogen removal rate.
TABLE 1 comparison of the biological modulus, COD removal Rate and Ammonia removal Rate of polyurethane filler of example 16 days before and after modification
| Contrast item | Day 1 | Day 2 | Day 3 | Day 4 | Day 5 | Day 6 |
| Modified filler biomembrane volume (mg/g) | 39.45 | 60.90 | 83.85 | 104.40 | 127.05 | 189.50 |
| Unmodified filler biomembrane content (mg/g) | 25.20 | 40.65 | 47.55 | 63.00 | 80.10 | 148.05 |
| COD removal rate of modified filler (%) | 53.96 | 56.64 | 60.97 | 67.84 | 81.21 | 86.19 |
| COD removal rate of unmodified filler (%) | 22.26 | 26.32 | 31.7 | 38.33 | 41.4 | 48.46 |
| Modified filler ammonia nitrogen removal rate (%) | 52.42 | 55.91 | 61.64 | 69.33 | 73.42 | 84.8 |
| Ammonia nitrogen removal rate of unmodified filler (%) | 21.08 | 26.13 | 32.72 | 38.74 | 45.5 | 60.81 |
According to the invention, the biological film amount and the biological film growth rate of the modified filler are higher than those of the unmodified filler, and the biological film amounts on each 1g of modified filler and the unmodified filler are 189.50mg and 148.05mg respectively on the 6 th day of measurement; the average daily growth amount of the biological film on each 1g of modified filler and unmodified filler is respectively 31.6mg/d and 24.7mg/d, the average daily growth amount of the biological film of the modified filler is increased by 28.0%, and the growth rate of the biological film is higher;
according to the invention, as shown in fig. 2 and table 1, the ammonia nitrogen treatment effect of the modified filler on wastewater is obviously better than that of the unmodified filler, the ammonia nitrogen removal rate of the modified filler reaches 84.8%, and the ammonia nitrogen removal rate of the unmodified filler is only 60.81%;
according to the invention, as shown in FIG. 3 and Table 1, the COD treatment effect of the modified filler on wastewater is obviously better than that of the unmodified filler, the COD removal rate of the modified filler reaches 86.19%, and the COD removal rate of the unmodified filler is only 48.46%;
the reason for the difference of the removal effect of the two fillers on COD and ammonia nitrogen in the wastewater is that apart from the obvious difference of the biological membrane amounts of the two fillers shown in figure 1, the surface of the modified filler is covered with Fe 2 O 3 In the related, the weak magnetic field effect can promote the vital activity of microorganisms, and simultaneously can promote the enzymatic reaction in cells to accelerate nutrient substances in the cell water.
From the above examples, the present invention provides a modification method for modifying polyurethane filler using hydroxyl radicals and iron ions generated during a high-level oxidation reaction using ferrous ions as a catalyst and peroxides as an oxidizing agent, which is suitable for use in aquatic organism treatment. Compared with the traditional polyurethane filler, the novel filler prepared by the modification method has larger specific surface area, has promotion effect on the adsorption and growth of microorganisms on the surface of the filler to form a biomembrane, can be applied to biomembrane method, and can improve the treatment efficiency of wastewater.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (8)
1. The preparation method of the modified polyurethane filler is characterized by comprising the following steps:
(1) Mixing a peroxide solution and a ferrous salt solution, and adjusting the pH value to obtain a mixed solution;
(2) Immersing polyurethane filler into the mixed solution for modification to obtain modified polyurethane filler.
2. The method for producing a modified polyurethane filler according to claim 1, wherein the pH is adjusted using a sodium hydroxide solution, a hydrochloric acid solution or a sulfuric acid solution in the step (1); the concentration of the sodium hydroxide solution is 0.1-0.5 mol/L; the concentration of the hydrochloric acid solution is 0.1-0.5 mol/L; the concentration of the sulfuric acid solution is 0.1-0.5 mol/L; the pH value of the mixed solution is less than or equal to 3.
3. The method for producing a modified polyurethane filler according to claim 1 or 2, wherein the concentration of the peroxide in the mixed solution of step (1) is 0.1 to 10mmol/L.
4. The method for producing a modified polyurethane filler according to claim 3, wherein the concentration of the ferrous salt in the mixed solution of the step (1) is 0.1 to 10mmol/L.
5. The method for producing a modified polyurethane filler according to claim 1 or 4, wherein the peroxide solution in the step (1) comprises a hydrogen peroxide solution, a peracetic acid solution or a sodium persulfate solution.
6. The method for producing a modified polyurethane filler according to claim 5, wherein the ferrous salt solution in the step (1) contains one or more of a ferrous sulfate solution and a ferrous chloride solution.
7. The method for producing a modified polyurethane filler according to claim 1, 2, 4 or 6, wherein the modification in the step (2) is carried out at 15 to 25℃for 1 to 4 hours.
8. The method for preparing modified polyurethane filler according to claim 7, wherein the modified polyurethane filler is obtained by drying after the modification in the step (2); the drying temperature is 100-120 ℃ and the drying time is 40-60 min.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202310927136.6A CN116813076A (en) | 2023-07-25 | 2023-07-25 | Preparation method of modified polyurethane filler |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310927136.6A CN116813076A (en) | 2023-07-25 | 2023-07-25 | Preparation method of modified polyurethane filler |
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