Preparation and application of antifungal hollow polymer nanospheres prepared by suspension polymerization method
Antifungal hollow polymer nanospheres were prepared by suspension polymerization, which solved the problem of unsatisfactory control of watermelon wilt in existing technologies and achieved a highly efficient and slow-release antifungal effect.
Patent Information
- Application Number
- CN202511449853.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-10-11
- Publication Date
- 2026-01-09
AI Technical Summary
Existing technologies are not very effective in controlling watermelon wilt, especially soil-borne diseases, and are difficult to effectively control diseases caused by Fusarium oxysporum.
Antifungal hollow polymer nanospheres were prepared by suspension polymerization. Spinosad was loaded by ion adsorption and suspension copolymerization, and double physical cross-linking nanospheres were formed by covalent and hydrogen bonding. The template was removed by template etching, resulting in antifungal hollow polymer nanospheres with good morphology and high specific surface area.
The prepared nanospheres exhibit good antibacterial and sustained-release properties against Fusarium oxysporum. The drug-loaded nanoparticles show higher toxicity than free spinosad at the same dosage, and can effectively control watermelon wilt.
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Figure CN121286465A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application belongs to the technical field of functional material preparation, and particularly relates to preparation and application of anti-fungal hollow polymer nanospheres by suspension polymerization. BACKGROUND
[0002] Watermelon is the second most popular fruit in the world after apple and banana, and is essential to human life. However, watermelon wilt occurs in all regions where watermelon is planted in the world, and is one of the most serious diseases in the production of watermelon in sunlight greenhouse, which can cause more than 70% reduction in watermelon yield. Large-scale outbreak of watermelon wilt seriously endangers the sustainable development of the industry. Fusarium oxysporum is the main pathogen of watermelon wilt, which harms plants from the root, causes vascular diseases, and causes plant death, and can occur throughout the growth period of the plant. At present, the main methods for preventing and controlling wilt are breeding disease-resistant varieties, using chemical pesticides and utilizing agricultural measures, but since wilt is a soil-borne disease, the effect is not ideal in prevention and control. In recent years, the application of high molecular materials in the agricultural field has made certain progress, and the development of efficient and safe new pesticide formulations by using polymer science, the improvement of the biological activity of the active ingredient and the target utilization rate, and the extension of the effective period have become the current research hotspot. In recent years, the application of polymer nanospheres in agriculture has attracted people's attention, and the research on inhibiting plant diseases has gradually become a hotspot. Studies have shown that polymer nanospheres can also load plant disease inducers to promote plant growth and induce the broad-spectrum disease resistance of plants. The present application uses ion adsorption and suspension copolymerization to load spinosad, and uses covalent bond and hydrogen bond to form a double-physical-crosslinking nanosphere. First, acrylic acid with a high carboxyl content is selected and adsorbed by ion bond and hydrogen bond. The present application widens the research direction of the application of high molecular materials in anti-fungal. SUMMARY
[0003] Therefore, one of the purposes of the present application is to provide a preparation method of anti-fungal hollow polymer nanospheres; the second purpose of the present application is to provide anti-fungal hollow polymer nanospheres; and the third purpose of the present application is to provide application of the anti-fungal hollow polymer nanospheres in catalyzing Diels-Alder reaction.
[0004] To achieve the above purposes, the present application provides the following technical solutions:
[0005] 1. A preparation method of anti-fungal hollow polymer nanospheres, the preparation method comprising the following steps:
[0006] (1) Preparation of PS@PAA / TEMED-SSD: the preparation process is as shown in Figure 1The PS, AA, CTAB were weighed and dispersed in 200 mL deionized water to obtain a uniformly dispersed precursor solution. Subsequently, 1 mL of 1.25 M TEMED and 1 mL of 0.08 M APS were added to the precursor solution under N2 protection. Then the three-necked flask was heated to 75 ℃, and 5 mL of 0.05 M divinylbenzene and 10 mL of 0.2 M SSD methanol solution were added dropwise, and the temperature was kept at 36 h. The PS@PAA / TEMED-SSD was obtained.
[0007] (2) Remove the hole template: the obtained PS@PAA / TEMED-SSD nanospheres were placed in a tetrahydrofuran and hydrochloric acid mixture (V THF :V HCl =1:3) for refluxing for 6 h to wash out the CTAB on the sphere wall. The solid was centrifuged, the pH was adjusted to 7-8 with ammonia water, and the product was washed with water (100 mL x 3) and ethanol (100 mL x 2) and naturally air-dried to obtain the mesoporous product.
[0008] (3) Remove the core template: the product was ultrasonically treated in a mixture of chloroform and toluene (2:1, v / v) for 15 min and stirred for 1 h. The white product was separated by centrifugation, washed with ethanol, and naturally air-dried to obtain the hollow mesoporous white magnetic mesoporous PAA / TEMED-SSDHns nanospheres.
[0009] Preferably, in step (1), the required proportions of PS, AA, and CTAB are 60-150 mg: 150-240 mg: 15-34 mg.
[0010] Preferably, in step (1), according to the preparation method of claim 1, in step (1), 200 ml of the precursor solution requires 0.5-1.7 ml of 0.8-1.7 M TEMED, 0.5-1.7 ml of 0.03-0.12 M APS, 5 ml of 0.03-0.07 M divinylbenzene, and 10 ml of 0.11-0.27 M SSD methanol solution.
[0011] Preferably, in step (1), according to the preparation method of claim 1, in step (1), the material is PS, which can be replaced by PAM or PAA in equal mass.
[0012] When replaced by PAA or PAM, the constant temperature heating is specifically 60-80 ℃.
[0013] Preferably, in step (1), the preparation method according to claim 1 is characterized in that, in step (1), the material is PS, which can be replaced by PAM or PAA in equal mass.
[0014] When replaced by PAA or PAM, the solvent added in the pre-solution is TEMED and APS.
[0015] Preferably, in step (1), the preparation method according to claim 1 is characterized in that, in step (1), the material is PS, which can be replaced by PAM or PAA in equal mass.
[0016] When replaced by PAM, the ratio of PAA, AA and CTAB is specifically 59-149: 151-238: 13-30.
[0017] When replaced by PAA, the ratio of PAA, AA and CTAB is specifically 63-152: 150-240: 12-34.
[0018] Preferably, in step (1), the preparation method according to claim 1 is characterized in that, in step (1), the dropping speed of divinylbenzene and SSD methanol solution is 1-2 drops per second.
[0019] Preferably, in step (2), the preparation method according to claim 1 is characterized in that, in step (2), the volume ratio of tetrahydrofuran to hydrochloric acid mixed solution is V THF :V HCl =0.5-1.5: 2.5-3.5.
[0020] Preferably, in step (3), the preparation method according to claim 1 is characterized in that, in step (3), the volume ratio of chloroform and toluene mixed solvent is V CHCl3 :V C7H8 =1-3: 0.5-1.5.
[0021] The beneficial effects of the present application are:
[0022] 1. The application discloses a preparation method of an antifungal hollow polymer nanosphere.
[0023] 2, The application also discloses an anti-fungal hollow polymer nanosphere, and the antibacterial performance of PAA / TEMED-SSD Hns on Fusarium oxysporum is determined by a growth rate method. The results show that the drug-loaded nanospheres have uniform particle size distribution, and the average particle size is about 520 nm, and the drug-loaded nanospheres have good sustained-release performance and pH response performance. The antibacterial experiment shows that the half effective concentration (EC 50 ) of the drug-loaded nanospheres (PAA / TEMED-SSD Hns) and SSD on Fusarium oxysporum is 29.12 μg / mL and 42.01 μg / mL, respectively, which indicates that the toxicity of PAA / TEMED-SSD Hns is higher than that of free SSD, and the nanospheres (PAA / TEMED-SSD) help to improve the toxicity of SSD. Therefore, the anti-fungal hollow polymer nanosphere has good application prospect in the anti-fungal direction.
[0024] Other advantages, objects, and features of the present application will be apparent to those skilled in the art from the following specification, in conjunction with the accompanying drawings, in which: BRIEF DESCRIPTION OF DRAWINGS
[0025] In order to make the objects, technical solutions and advantages of the present application clearer, the preferred embodiments of the present application will be described in detail below with reference to the accompanying drawings, in which:
[0026] Figure 1 A flow chart for preparing the anti-fungal hollow polymer nanosphere PAA / TEMED-SSD Hns of the present application;
[0027] Figure 2 A SEM image of the anti-fungal hollow polymer nanosphere PAA / TEMED-SSD Hns prepared in Example 1;
[0028] Figure 3 A TEM image of the anti-fungal hollow polymer nanosphere PAA / TEMED-SSD Hns prepared in Example 1;
[0029] Figure 4 A pore size distribution graph of the anti-fungal hollow polymer nanosphere PAA / TEMED-SSD Hns prepared in Example 1;
[0030] Figure 5 An infrared spectrum graph of the anti-fungal hollow polymer nanosphere PAA / TEMED-SSD Hns prepared in Example 1;
[0031] Figure 6Cumulative release profile of the antifungal hollow polymer nanospheres PAA / TEMED-SSD Hns prepared in Example 1 at different pH.
[0032] Figure 7 Antifungal activity of a) PAA, b) SSD and c) the antifungal hollow polymer nanospheres PAA / TEMED-SSD Hns prepared in Example 1 against Fusarium oxysporum. DETAILED DESCRIPTION
[0033] The present application is herein described, by way of example only, with reference to certain embodiments thereof. It is to be understood that variations and modifications will be apparent to those skilled in the art and that the scope of the present application encompasses all such obvious variations and modifications. Where specific details are given, it is to be understood that these are given by way of illustration only and that these specific details can not be necessary to the practice of the application. It is to be understood that the features of the following examples can be combined with each other, where possible, without conflict.
[0034] Example 1
[0035] An antifungal hollow polymer nanosphere, the specific preparation method is as follows:
[0036] 1. Preparation of PS@PAA / TEMED-SSD
[0037] PS@PAA / TEMED-SSD was prepared by a two-step method, and the preparation process is shown in Figure 1 . 100 mg of PS, 200 mg of AA, and 24 mg of CTAB were weighed and dispersed in 200 mL of deionized water to obtain a uniform precursor solution. Subsequently, under N2 protection, 1 mL of 1.25 M TEMED and 1 mL of 0.08 M APS were added to the precursor solution in sequence to form an initiation system. Then, the three-necked flask was heated to 75 °C, and 5 mL of 0.05 M divinylbenzene and 10 mL of 0.2 M SSD methanol solution were added dropwise, and the temperature was kept at 36 °C for 36 h. Thus, PS@PAA / TEMED-SSD was obtained.
[0038] 2. Preparation of PAA / TEMED-SSD Hns
[0039] (1) The obtained PS@PAA / TEMED-SSD nanospheres were placed in a tetrahydrofuran and hydrochloric acid mixture (V THF :V HCl =1:3) for refluxing for 6 h to wash out the CTAB on the sphere wall. The solid was centrifuged, the pH was adjusted to 7 with ammonia water, and then washed with water (100 mL x 3) and ethanol (100 mL x 2), and naturally air-dried to obtain the mesoporous product.
[0040] (2) Chloroform: toluene (2:1, v / v) mixed solvent, ultrasonic for 15 min, stirring for 1 h. Centrifugal separation, the white product was washed with ethanol and naturally air-dried to obtain hollow mesoporous white magnetic mesoporous PAA / TEMED-SSD Hns nanospheres.
[0041] Continue stirring for 1 h, centrifugal separation after washing with acetone for several times and natural ventilation drying for 4 h to obtain anti-fungal hollow polymer nanospheres.
[0042] Example 2
[0043] An anti-fungal hollow polymer nanosphere, the specific preparation method is as follows:
[0044] 1. Preparation of PS@PAA / TEMED-SSD
[0045] PS@PAA / TEMED-SSD is prepared by a two-step method, and the preparation process is as shown in Figure 1 . 100 mg of PS, 200 mg of AA, and 24 mg of CTAB were dispersed in 200 mL of deionized water to obtain a uniformly dispersed precursor solution. Then, under N2 protection, 1 mL of 1.14 M TEMED and 1 mL of 0.09 M APS were added to the precursor solution in sequence. Then, the three-necked flask was heated to 85 ℃, and 5 mL of 0.07 M divinylbenzene and 10 mL of 0.31 M SSD methanol solution were added dropwise, and the temperature was kept for 36 h. PS@PAA / TEMED-SSD was obtained.
[0046] 2. Preparation of PAA / TEMED-SSD Hns
[0047] (1) The obtained PS@PAA / TEMED-SSD nanospheres were placed in a tetrahydrofuran and hydrochloric acid mixture (V THF :V HCl =1:3) for 6 h of reflux, and the CTAB on the ball wall was washed out. The solid was centrifuged, ammonia was added to adjust the Ph to 8, and water was washed (100 mL x 3), ethanol was washed (100 mL x 2), and the product was naturally air-dried to obtain the mesoporous product.
[0048] (2) Chloroform: toluene (2:1, v / v) mixed solvent, ultrasonic for 15 min, stirring for 1 h. Centrifugal separation, the white product was washed with ethanol and naturally air-dried to obtain hollow mesoporous white magnetic mesoporous PAA / TEMED-SSD Hns nanospheres.
[0049] Continue stirring for 1 h, centrifugal separation after washing with acetone several times, and natural ventilation drying for 4 h to obtain the anti-fungal hollow polymer nanospheres.
[0050] Example 3
[0051] An anti-fungal hollow polymer nanosphere, the specific preparation method is as shown below:
[0052] 1. Preparation of PS@PAA / TEMED-SSD
[0053] PS@PAA / TEMED-SSD is prepared by a two-step method, and the preparation process is as shown in Figure 1 . 100 mg of PS, 200 mg of AA, and 24 mg of CTAB are weighed and dispersed in 200 mL of deionized water to obtain a uniformly dispersed precursor solution. Then, under N2 protection, 1 mL of 1.10 M TEMED and 1 mL of 0.07 M APS initiation system are sequentially added to the precursor solution. Then, the three-necked flask is heated to 65 ℃, and 5 mL of 0.11 M divinylbenzene and 10 mL of 0.29 M SSD methanol solution are added dropwise, and the temperature is kept at 36 h. PS@PAA / TEMED-SSD is obtained.
[0054] 2. Preparation of PAA / TEMED-SSD Hns
[0055] (1) The obtained PS@PAA / TEMED-SSD nanospheres are placed in a tetrahydrofuran and hydrochloric acid mixture (V THF :V HCl =1:3) for refluxing for 6 h to wash out the CTAB in the wall of the nanospheres. The solid is centrifuged, ammonia is added to adjust the pH to 7, and water washing (100 mL x 3) and ethanol washing (100 mL x 2) are performed. The mesoporous product is obtained by natural air drying.
[0056] (2) In a mixture of chloroform and toluene (2:1, v / v), ultrasonic for 15 min, and stirring for 1 h. Centrifugal separation, the obtained white product is washed with ethanol and naturally air dried to obtain the hollow mesoporous white magnetic mesoporous PAA / TEMED-SSD Hns nanospheres.
[0057] Continue stirring for 1 h, centrifugal separation after washing with acetone several times, and natural ventilation drying for 4 h to obtain the anti-fungal hollow polymer nanospheres.
[0058] Example 4
[0059] An anti-fungal hollow polymer nanosphere, the specific preparation method is as shown below:
[0060] 1. Preparation of PS@PAA / TEMED-SSD
[0061] PS@PAA / TEMED-SSD was prepared by a two-step method, as shown in the following scheme. Figure 1 The precursor solution was prepared by dispersing 100 mg of PS, 200 mg of AA, and 24 mg of CTAB in 200 mL of deionized water. Then, 1 mL of 1.09 M TEMED and 1 mL of 0.10 M APS were added to the precursor solution under N2 protection. The three-necked flask was then heated to 75 °C, and 5 mL of 0.09 M divinylbenzene and 10 mL of 0.27 M SSD methanol solution were added dropwise. The temperature was maintained at 75 °C for 36 h to obtain PS@PAA / TEMED-SSD.
[0062] 2. Preparation of PAA / TEMED-SSD Hns
[0063] (1) The obtained PS@PAA / TEMED-SSD nanospheres were placed in a mixture of tetrahydrofuran and hydrochloric acid (V THF :V HCl = 1:3) for refluxing for 6 h to wash out the CTAB on the sphere wall. The solid was centrifuged, the pH was adjusted to 7 with ammonia water, and the product was washed with water (100 mL x 3) and ethanol (100 mL x 2) and then naturally air-dried to obtain the mesoporous product.
[0064] (2) The obtained white product was washed with ethanol and then naturally air-dried to obtain the hollow mesoporous PAA / TEMED-SSD Hns nanospheres.
[0065] The stirring was continued for 1 h, and the product was washed with acetone, centrifuged, and then naturally air-dried for 4 h to obtain the antifungal hollow polymer nanospheres.
[0066] Examples 5-6
[0067] The implementation method and the synthesis conditions were the same as in Example 1, except that the “ammonia water” used for adjusting the pH in step (1) of Example 1 was replaced by “20% sodium hydroxide solution” and “triethylamine”, respectively, to prepare the antifungal hollow polymer nanospheres.
[0068] Examples 7-8
[0069] The implementation method and the synthesis conditions were the same as in Example 1, except that the “mixture of tetrahydrofuran and hydrochloric acid (V THF :V HCl = 1:3)” used in step (1) of Example 1 was replaced by “VTHF : V HCl =2:5" and "V THF : V HCl =1:2", antifungal hollow polymer nanospheres were prepared.
[0070] Examples 9~10
[0071] The implementation method and the synthesis condition were the same as those of Example 1, except that "chloroform:toluene (2:1, v / v) mixed solvent" used in "100 mg PS, 200 mg AA, 24 mg CTAB" of step (1) of Example 1 was replaced by "5:2, v / v" and "4:3, v / v", respectively, to prepare antifungal hollow polymer nanospheres.
[0072] Examples 11~12
[0073] The implementation method and the synthesis condition were the same as those of Example 1, except that "100 mg PS" used in "100 mg PS, 200 mg AA, 24 mg CTAB" of step (1) of Example 1 was replaced by "100 mg PAA" and "100 mg PAM", respectively, to prepare antifungal hollow polymer nanospheres.
[0074] Performance test
[0075] 1. Physical property test of various products in examples
[0076] Figure 6 Cumulative release curve of antifungal hollow polymer nanospheres PAA / TEMED-SSD Hns prepared in Example 1 at different pH.
[0077] Figure 7 Antifungal hollow polymer nanospheres prepared in Examples 1, 2, and 3 against Fusarium oxysporum.
[0078] Figure 2 SEM image of antifungal hollow polymer nanospheres PAA / TEMED-SSD Hns prepared in Example 1.As can be seen from the SEM image, the size of the antifungal hollow polymer nanospheres prepared in Example 1 was 519±21 nm, and the surface of the antifungal hollow polymer nanospheres was relatively smooth. Figure 2
[0079] TEM image of an antifungal hollow polymer nanosphere PAA / TEMED-SSD Hns prepared in Example 1.As can be seen from the TEM image, the antifungal hollow polymer nanosphere prepared in Example 1 was a hollow sphere. Figure 3 Figure 3
[0080] Figure 4The image shows the pore size distribution of the antifungal hollow polymer nanospheres PAA / TEMED-SSD Hns prepared in Example 1. Figure 4 As shown in the mid-spectrum, the mesopores of the antifungal hollow polymer nanospheres prepared in Example 1 are distributed between 2 and 10 nm. Due to the presence of numerous mesopores, the specific surface area of the antifungal hollow polymer nanospheres is 325.0 m². 2 s -1 It has good drug storage and sustained-release function.
[0081] Figure 5 The image shows the infrared spectrum of the antifungal hollow polymer nanospheres PAA / TEMED-SSD Hns prepared in Example 1. From... Figure 5 It can be observed that dry samples of PAA and PAA / TEMED-SSD Hns were characterized using FTIR spectroscopy. For pure PAA material, 3191 (OH stretching vibration), 1650 cm⁻¹ -1 The peaks represent the characteristic absorption of the -CO- group, at 2930 and 1449 cm⁻¹. -1 The two peaks at this point correspond to the tensile and bending vibrations of -CH2-, respectively. After introducing SSD into the nanospheres, the characteristic peak of -CONH2 shifted to 3332 cm⁻¹. -1 This can be used to determine changes in hydrogen bonding, and thus determine whether SSD and PAA have formed hydrogen bonds.
[0082] Similarly, the antifungal hollow polymer nanospheres prepared in other embodiments were subjected to the above-mentioned various performance tests, and the results were similar to those of the antifungal hollow polymer nanospheres prepared in Example 1 above. This shows that the preparation method of the present invention can indeed prepare antifungal hollow polymer nanospheres with good crystallinity, high specific surface area, low density, tight structural arrangement and unique hollow shell structure.
[0083] 2. Antibacterial applications
[0084] PAA / TEMED-SSD Hns sustained-release performance Figure 6 The sustained-release curves of PAA / TEMED-SSD Hns at different pH values are shown. At pH 3.5 and 6.5, PAA / TEMED-SSD Hns exhibited two phases: a burst release phase and a sustained-release phase. The burst release phase facilitates rapid action of the drug on pests and diseases, while the sustained-release phase allows for gradual release of the drug to maintain a certain concentration range, thus providing a sustained effect in killing pests and diseases. Figure 6It can be seen that the cumulative release amount of PAA / TEMED-SSD Hns at pH = 3.5 is larger than that at pH = 6.5, which is mainly determined by the structure of the nanosphere. It is easy to be acid-base adsorbed and decomposed under the condition of strong acid, resulting in a larger cumulative release amount. Under the condition of pH = 6.5, the cumulative release amount can reach 50% after 2.4 h, and then slowly release.
[0085] Toxicity and antibacterial performance of PAA / TEMED-SSD Hns: The antifungal activity of PAA / TEMED-SSD Hns on Fusarium oxysporum was measured by mycelium growth rate method, and the results are shown in Figure 7 When the concentration of spinosad drug is 20 mg L -1 , the 14-day inhibition rate of PAA / TEMED-SSD Hns on Fusarium oxysporum is 8.94% higher than that of SSD, which indicates that PAA / TEMED-SSD Hns has higher antifungal activity on Fusarium oxysporum under the same dose of spinosad.
[0086] Finally, it should be pointed out that the above examples are only used to illustrate the technical solutions of the present application and are not limiting. Although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can be modified or replaced by equivalents without departing from the purpose and scope of the technical solutions, which should be covered in the scope of the claims of the present application.
Claims
1. A method for preparing an antifungal hollow polymeric nanosphere, characterized by, The preparation method comprises the following steps: (1) Preparation of PS@PAA / TEMED-SSD: PS, AA, CTAB are dispersed in deionized water to prepare a precursor solution. Then, TEMED and APS are sequentially added to the precursor solution under N2 protection. Subsequently, heating to 65-85 ℃, dropwise addition of divinylbenzene and SSD methanol solution, constant temperature for 30-40 h to obtain PS@PAA / TEMED-SSD. (2) Preparation of PAA / TEMED-SSD Hns: The PS@PAA / TEMED-SSD in step (1) is placed in a mixture of tetrahydrofuran and hydrochloric acid and refluxed for 6 h to separate out CTAB. Centrifugation to obtain a solid, adjust Ph=7-8, water washing, ethanol washing, and then natural air drying to obtain a mesoporous product. Subsequently, in a mixed solvent of chloroform and toluene, ultrasonic for 5-25 min, stirring for 0.5-2 h. Centrifugation, the obtained white product is washed with ethanol and then naturally air dried to obtain a hollow mesoporous white magnetic mesoporous PAA / TEMED-SSD Hns nanosphere.
2. The production method according to claim 1, characterized by, In step (1), the required proportions of PS, AA, CTAB are 60-150: 150-240: 15-34.
3. The preparation method according to claim 1, characterized in that, In step (1), 200 ml of the precursor solution requires 0.5-1.7 ml of 0.8-1.7 M TEMED, 0.5-1.7 ml of 0.03-0.12 M APS, 5 ml of 0.03-0.07 M divinylbenzene, and 10 ml of 0.11-0.27 M SSD methanol solution.
4. The method of claim 1, wherein, In step (1), the material is PS, which can be replaced by PAM or PAA in equal mass; When replaced by PAA or PAM, the constant temperature heating is specifically 60-80 ℃.
5. The preparation method according to claim 1, characterized in that, In step (1), the material is PS, which can be replaced by PAM or PAA in equal mass; When replaced by PAA or PAM, the precursor solution still adds TEMED and APS.
6. The method of claim 1, wherein, In step (1), the material is PS, which can be replaced by PAM or PAA in equal mass; When replaced by PAM, the proportions of PAA, AA, CTAB are specifically 59-149: 151-238: 13-30. When replaced by PAA, the proportions of PAA, AA, CTAB are specifically 63-152: 150-240: 12-34.
7. The preparation method according to claim 1, characterized in that, In step (1), the dropwise addition rate of divinylbenzene and SSD methanol solution is 1-2 drops / s.
8. The preparation method according to claim 1, characterized in that, In step (2), V THF : V HCl = 0.5~1.5 : 2.5~3.
5.
9. The method of claim 1, wherein, In step (2), the V of chloroform and toluene mixed solvent is 1~3 CHCl3 : VC7H8 = 1~3 : 0.5~1.5.