Preparation method of antibacterial super-crosslinked porous polymeric material
By constructing antibacterial super-cross-linked porous polymer materials, the problem of uncontrollable morphology and performance of porous organic polymer materials was solved, the porosity, specific surface area and antibacterial properties of the materials were improved, the stability under light and heating conditions was ensured, and the scope of application was expanded.
Patent Information
- Application Number
- CN202510802841.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-16
- Publication Date
- 2025-10-10
AI Technical Summary
The morphology, structure and properties of existing porous organic polymer materials cannot be controlled, and the porosity, specific surface area, biocompatibility and functionalization difficulty are insufficient. Silver-based antibacterial agents are expensive and easily inactivated by light and heating, which limits their application range.
Low-functionality rigid aromatic compounds are used as monomers, combined with external crosslinkers and Friedel-Crafts reaction to construct a super-crosslinked porous polymer network, and silver ions are introduced to construct an antibacterial super-crosslinked porous polymer material through Friedel-Crafts reaction.
The regulation of the porous structure is achieved, the material performance and antibacterial effect are improved, the stability problem of silver-based antibacterial agents under light and heating conditions is solved, and a more advantageous antibacterial material option is provided.
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Figure CN120757726A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of porous polymeric materials, in particular to a preparation method of antibacterial super-crosslinked porous polymeric materials. BACKGROUND
[0002] In recent years, porous organic polymers (POPs) as a new type of porous framework material have been rapidly developed since they were first reported in 2005. These materials have shown broad application prospects in gas adsorption, separation, catalysis, and sensing due to their unique pore structure and controllable physical and chemical properties. At the same time, silver as an inorganic broad-spectrum antibacterial agent has been favored by various industries due to its excellent antibacterial performance. Based on the antibacterial mechanism of silver, various silver-based antibacterial products have been developed on the market, such as silver-loaded molecular sieve antibacterial agents, silver-loaded phosphate antibacterial agents, and silver-loaded oxide antibacterial agents, which are widely used in medical, health, and food preservation fields.
[0003] However, there are some problems in the existing porous organic polymers that need to be solved, such as the uncontrollability of their morphology, structure, and performance, which limits their application range. Specifically, there are deficiencies in porosity, specific surface area (SBET), biocompatibility, and functionalization difficulty. In addition, using silver alone as an antibacterial agent also has obvious defects, such as high cost of silver materials and loss of antibacterial activity under conditions such as light and heat, which also restricts its widespread application in practical applications.
[0004] To solve the above problems, the present application provides a preparation method of antibacterial super-crosslinked porous polymeric materials. By using a rigid aromatic compound with low functionality as a monomer raw material, combined with external crosslinking agents and Friedel-Crafts reaction to construct a super-crosslinked porous polymer network, the porous structure of the super-crosslinked POPs material is adjusted, which not only improves the performance and application range of the material, but also significantly enhances its antibacterial effect, providing a more advantageous material selection for related fields. SUMMARY
[0005] The purpose of the present application is to provide a preparation method of antibacterial super-crosslinked porous polymeric materials to overcome the deficiencies in the prior art. To achieve the above purpose, the technical scheme adopted by the present application is as follows:
[0006] The present application provides a preparation method of antibacterial super-crosslinked porous polymeric materials, comprising the following steps:
[0007] Step one, under N2 environment, anhydrous ferric chloride, tetramethyltetraphenylcyclotetrasiloxane, and methylal are added to a round-bottom flask containing 1,2-dichloroethane to obtain a reaction mixture;
[0008] Step 2: heating the reaction mixture under stirring conditions to raise the temperature of the reaction system to 80° C.-90° C. and maintaining the reaction under reflux. After the reaction is completed, heating is stopped to obtain a hyper-crosslinked porous polymer intermediate;
[0009] Step 3: sequentially subjecting the hyper-crosslinked porous polymer intermediate to cooling, filtering, washing, extraction, and drying to obtain a hyper-crosslinked porous polymer material;
[0010] Step 4: uniformly dispersing the hyper-crosslinked porous polymer material in ethanol and ultrasonically treating the mixture to form a mixed solution; then adding a silver nitrate solution to the mixed solution at room temperature to carry out a light-shielding reaction at room temperature to obtain an antibacterial hyper-crosslinked porous polymer material intermediate;
[0011] Step 5: Add sodium borohydride solution to the antibacterial hyper-crosslinked porous polymer intermediate and immediately centrifuge. After centrifugation, retain the bottom precipitate, wash the precipitate several times with ethanol and deionized water, and then freeze-dry to obtain the antibacterial hyper-crosslinked porous polymer.
[0012] Further, the molar ratio of methylal to tetramethyltetraphenylcyclotetrasiloxane is 6 to 12:1;
[0013] The molar ratio of the anhydrous ferric chloride to the tetramethyltetraphenylcyclotetrasiloxane is 4 to 5:1.
[0014] Furthermore, in the step three, the washing treatment is to use an organic solvent for several washings, the extraction treatment is to use a Soxhlet extractor for 40h-50h, and the drying treatment is to dry in a vacuum oven at 50°C-70°C for 20h-30h.
[0015] Furthermore, in the step 4, the molar ratio of the hyper-crosslinked porous polymer material to the silver nitrate solution is 1:10-11, and the amount of the silver nitrate solution added is 50 mL-60 mL.
[0016] Furthermore, in step five, the amount of the sodium borohydride solution added is 10 mL-20 mL, and the molar concentration of the sodium borohydride solution is 0.5 mol / L-1 mol / L.
[0017] Furthermore, the freeze-drying process uses a freeze dryer.
[0018] Furthermore, the freeze-drying treatment time is 13h-16h.
[0019] Furthermore, the molar concentration of the silver nitrate solution is 0.2 mol / L-0.5 mol / L.
[0020] The present application adopts the above technical scheme, and has the following technical effects compared with the prior art.
[0021] The beneficial effects of the present application mainly include the following aspects: first, the antibacterial performance is excellent, by introducing silver ions into the super-crosslinked porous polymeric material, using the action of silver ions and bacterial cell membrane protein sulfhydryl (-SH) and catalyzing active oxygen (ROS) to realize the broad-spectrum, long-lasting and efficient antibacterial effect, and the present application has good stability, solves the problem that the traditional silver-based antibacterial agent is easy to be inactivated under the conditions of light and heating, ensures long-term stable antibacterial effect, and the present application has obvious advantages in antibacterial performance, structure control, cost control and environmental adaptability, and has wide application prospect. BRIEF DESCRIPTION OF DRAWINGS
[0022] Figure 1 is the infrared IR contrast spectrum of the antibacterial super-crosslinked porous polymeric material with different proportions;
[0023] Figure 2 is the nitrogen adsorption-desorption curve graph of the antibacterial super-crosslinked porous polymeric material with different proportions at 77K;
[0024] Figure 3 is the pore size distribution graph of the antibacterial super-crosslinked porous polymeric material with different proportions;
[0025] Figure 4 is the carbon dioxide adsorption curve graph of the antibacterial super-crosslinked porous polymeric material with different proportions at 273K. DETAILED DESCRIPTION
[0026] The specific embodiments of the present application will be described in detail below.
[0027] Unless otherwise defined, the technical terms or scientific terms used in the claims and the specification should be understood as the general meaning understood by those skilled in the art in the technical field to which the present application belongs.
[0028] The "includes" or similar words used in the patent application specification and claims of the present application mean that the objects appearing before the "includes" cover the objects appearing after the "includes" or its equivalent objects, and do not exclude other objects.
[0029] The numerical values recited in the application include all values from and including the lower and the upper limits of the range if the lower limit is not zero and the upper limit is not infinity. For ranges including values which are out of the normal range, for example, 1 to 100, 10 to 90, 20 to 80, 5 to 95, 14 to 76, 23 to 67, 32 to 58, 41 to 49, etc., any number which falls within the specified range should be considered as being expressly stated. For ranges including values less than one, 0.0001, 0.001, 0.01, or 0.1 are understood as being expressly stated. The above examples are merely illustrative, and it will be understood that the description in the specification is intended to cover all possible combinations of the range values.
[0030] Example 1
[0031] The present embodiment provides a method for preparing an antibacterial super-crosslinked porous polymeric material, comprising the following steps:
[0032]
[0033] Step one, under N2 environment, anhydrous ferric chloride (FeCl3) (4.0 mmol, 0.650 g), tetramethyltetraphenylcyclotetrasiloxane [(MePhSiO)4] (1.0 mmol, 0.545 g) and formaldehyde (FDA) (10 mmol, 0.7611 g) were added into a round bottom flask containing 40 mL of 1,2-dichloroethane (DCE) to obtain a reaction mixture;
[0034] The reaction mixture was heated under stirring, and the temperature of the reaction system was raised to 80°C and kept in a reflux state for 10 h. After the reaction was completed, the heating was stopped, and a super-crosslinked porous polymeric intermediate was obtained.
[0035] Step two, the super-crosslinked porous polymeric intermediate was sequentially subjected to cooling treatment, suction filtration treatment, and washed with methanol for 3 times. Then, the washed product was extracted by a Soxhlet extractor for 48 h. The extracted product was dried in a vacuum oven at 60°C for 24 h to obtain a super-crosslinked porous polymeric material.
[0036] Step three, 1 mmol of the prepared super-crosslinked porous polymeric material was uniformly dispersed in 20 mL of ethanol, and ultrasonic treatment was performed for 2 h to form a mixed solution.
[0037] To the mixed solution, 50 mL of silver nitrate solution with a concentration of 0.2 mol / L was added, and a light shielding reaction was performed at room temperature for 2 h to obtain an antibacterial super-crosslinked porous polymeric material intermediate.
[0038] Step four, 10 mL of 0.5 mol / L sodium borohydride solution was added to the above antibacterial hypercrosslinked porous polymeric material intermediate, and immediately centrifuged;
[0039] After centrifugation, the bottom precipitate was retained, and the precipitate was washed with ethanol and deionized water for 3 times.
[0040] Finally, the washed precipitate was freeze-dried for 15 h using a freeze dryer to obtain the antibacterial hypercrosslinked porous polymeric material (POPs-3).
[0041] In this embodiment 1, by adjusting the molar ratio of methylal to tetramethyltetraphenylcyclotetrasiloxane to 10:1, the maximum specific surface area (877 m 2 / g) and suitable pore size distribution were obtained, which increased the contact probability with microorganisms, and the antibacterial rate of Escherichia coli in Example 1 was more than 98.8%.
[0042] Example 2
[0043] The present embodiment provides a preparation method of an antibacterial hypercrosslinked porous polymeric material, and the specific steps are as follows:
[0044] Step one, under N2 environment, anhydrous ferric chloride (4.0 mmol, 0.650 g), tetramethyltetraphenylcyclotetrasiloxane (1.0 mmol, 0.545 g) and methylal (6 mmol, 0.4567 g) were added to a round-bottom flask containing 40 mL of 1,2-dichloroethane to obtain a reaction mixture.
[0045] The reaction mixture was heated under stirring, and the temperature of the reaction system was raised to 80℃ and kept in reflux state for 10 h. After the reaction was completed, the heating was stopped to obtain a hypercrosslinked porous polymeric intermediate.
[0046] Step two, the above hypercrosslinked porous polymeric intermediate was sequentially subjected to cooling treatment, suction filtration treatment, and washed with methanol for 3 times, and then the washed product was extracted using a Soxhlet extractor for 48 h. The extracted product was dried in a vacuum oven at 60℃ for 24 h to obtain a hypercrosslinked porous polymeric material.
[0047] Step three, 1 mmol of the above prepared hypercrosslinked porous polymeric material was uniformly dispersed in 20 mL of ethanol, and ultrasonic treatment was performed for 2 h to form a mixed solution.
[0048] 50 mL of 0.2 mol / L silver nitrate solution was added to the above mixed solution, and the reaction was carried out at room temperature for 2 h in the dark to obtain an antibacterial hypercrosslinked porous polymeric material intermediate.
[0049] Step 4: Add 10 mL of 0.5 mol / L sodium borohydride solution to the antibacterial hyper-crosslinked porous polymer intermediate and immediately centrifuge;
[0050] After centrifugation, the bottom precipitate was retained and washed three times with ethanol and deionized water respectively;
[0051] Finally, the washed precipitate was freeze-dried for 15 hours using a freeze dryer to obtain an antibacterial hyper-cross-linked porous polymer material (POPs-1).
[0052] Example 3
[0053] This embodiment provides a method for preparing an antibacterial hyper-crosslinked porous polymer material, and the specific steps are as follows:
[0054] Step 1: Under N2 environment, anhydrous ferric chloride (4.0 mmol, 0.650 g), tetramethyltetraphenylcyclotetrasiloxane (1.0 mmol, 0.545 g) and methylal (8 mmol, 0.6089 g) were added to a round-bottom flask containing 40 mL of 1,2-dichloroethane to obtain a reaction mixture;
[0055] The reaction mixture was heated under stirring conditions to raise the temperature of the reaction system to 80° C. and maintained in a reflux state for 10 hours. After the reaction was completed, the heating was stopped to obtain a super-crosslinked porous polymer intermediate.
[0056] Step 2: The above-mentioned hyper-cross-linked porous polymer intermediate is cooled and filtered in sequence, and washed with methanol three times. The washed product is then extracted using a Soxhlet extractor for 48 hours. The extracted product is dried in a vacuum oven at 60°C for 24 hours to obtain a hyper-cross-linked porous polymer material.
[0057] Step 3: Weigh 1 mmol of the hyper-crosslinked porous polymer material prepared above and evenly disperse it in 20 mL of ethanol, and perform ultrasonic treatment for 2 hours to form a mixed solution;
[0058] 50 mL of 0.2 mol / L silver nitrate solution was added to the mixed solution, and the mixture was reacted under light shielding at room temperature for 2 h to obtain an antibacterial super-crosslinked porous polymer material intermediate.
[0059] Step 4: Add 10 mL of 0.5 mol / L sodium borohydride solution to the antibacterial hyper-crosslinked porous polymer intermediate and immediately centrifuge;
[0060] After centrifugation, the bottom precipitate was retained and washed three times with ethanol and deionized water respectively;
[0061] Finally, the washed precipitate was freeze-dried for 15 h to obtain the antibacterial supercrosslinked porous polymeric material (POPs-2).
[0062] Example 4
[0063] The present example provides a method for preparing an antibacterial supercrosslinked porous polymeric material, and the specific steps are as follows:
[0064] Step one, under N2 environment, anhydrous ferric chloride (4.0 mmol, 0.650 g), tetramethyltetraphenylcyclotetrasiloxane (1.0 mmol, 0.545 g) and methyl formate (12 mmol, 0.913 g) were added to a round-bottom flask containing 40 mL of 1,2-dichloroethane to obtain a reaction mixture;
[0065] The reaction mixture was heated under stirring, and the temperature of the reaction system was raised to 80°C and kept at reflux state for 10 h. After the reaction was completed, the heating was stopped to obtain a supercrosslinked porous polymeric intermediate.
[0066] Step two, the above supercrosslinked porous polymeric intermediate was sequentially subjected to cooling treatment, suction filtration treatment, and washed with methanol for 3 times. Then, the washed product was extracted using a Soxhlet extractor for 48 h. The extracted product was dried in a vacuum oven at 60°C for 24 h to obtain a supercrosslinked porous polymeric material.
[0067] Step three, 1 mmol of the prepared supercrosslinked porous polymeric material was uniformly dispersed in 20 mL of ethanol and subjected to ultrasonic treatment for 2 h to form a mixed solution.
[0068] To the above mixed solution, 50 mL of silver nitrate solution with a concentration of 0.2 mol / L was added, and the reaction was carried out at room temperature for 2 h to obtain an antibacterial supercrosslinked porous polymeric material intermediate.
[0069] Step four, 10 mL of sodium borohydride solution with a concentration of 0.5 mol / L was added to the above antibacterial supercrosslinked porous polymeric material intermediate, and immediately centrifuged.
[0070] After centrifugation, the bottom precipitate was retained, and the precipitate was washed with ethanol and deionized water for 3 times.
[0071] Finally, the washed precipitate was freeze-dried for 15 h to obtain the antibacterial supercrosslinked porous polymeric material (POPs-2).
[0072] Blank comparative example
[0073] The present blank comparative example provides a method for preparing a non-silver-loaded supercrosslinked porous polymeric material (POPs-0), and the specific steps are as follows:
[0074] Step one, under the protection of N2 atmosphere, anhydrous ferric chloride (FeCl3, 4.0 mmol, 0.650 g), tetramethyltetraphenylcyclotetrasiloxane [(MePhSiO)4] (1.0 mmol, 0.545 g) and methylal (10 mmol, 0.7611 g), i.e. the molar ratio of methylal to tetramethyltetraphenylcyclotetrasiloxane [(MePhSiO)4] is 10:1, were added to a round-bottom flask containing 40 mL of 1,2-dichloroethane (DCE), and a uniform reaction mixture was obtained after thorough mixing.
[0075] Step two, the above reaction mixture was placed under stirring conditions, gradually heated to 80°C, and kept in a reflux state for 10 h. During the reaction, the reaction mixture was fully contacted under the action of stirring and reflux to ensure complete reaction. After the reaction was completed, the heating was stopped, and a hypercrosslinked porous polymeric intermediate was obtained.
[0076] Step three, the obtained hypercrosslinked porous polymeric intermediate was sequentially subjected to cooling treatment, suction filtration treatment, and washed with methanol for 3 times to remove unreacted raw materials and by-products, then the washed product was extracted using a Soxhlet extractor for 48 h to further remove residual impurities. Finally, the extracted product was placed in a vacuum oven at 60°C for drying for 24 h, and a silver-unloaded hypercrosslinked porous polymeric material (POPs-0) was obtained.
[0077] The blank comparative example is set to compare the effect of silver loading on the antibacterial performance of the hypercrosslinked porous polymeric material, and the performance of the silver-loaded hypercrosslinked porous polymeric material (such as the POPs-3 of Example 1) can be more clearly evaluated to assess the effect of silver ions in antibacterial applications.
[0078] The following Table 1 is a table of several key physical and chemical parameters and performance indicators of the hypercrosslinked porous polymeric materials (POPs) prepared in different proportions:
[0079] Table 1
[0080] <![CDATA[S BET / m 2 g -1 ]]> V total / cm 3 g -1 ]]> V micro / cm 3 g -1 ]]> <![CDATA[V micro / V total ]]> CO2 uptake / cm 3 g -1 ]]> Example 2 POPs-1 672 0.62 0.07 0.10 40.4 Example 3 POPs-2 732 0.65 0.08 0.12 42.9 Example 1 POPs-3 877 1.34 0.07 0.05 44.8 Example 4 POPs-4 642 0.55 0.06 0.11 37.2
[0081] The following Table 2 is a comparison table of the antibacterial performance tests of Example 1, Example 2, Example 3, Example 4, and the blank comparative example:
[0082] Table 2
[0083]
[0084] In conclusion, the beneficial effects of the present application mainly reflect in the following aspects: one is excellent antibacterial performance, by introducing silver ions in the super cross-linked porous polymeric material, using the action of silver ions and bacterial cell membrane protein sulfhydryl (-SH) and catalytic production of reactive oxygen species (ROS), realize the broad-spectrum, long-lasting and efficient antibacterial effect, and the present application has good stability, solves the problem that the traditional silver-based antibacterial agent is easy to be inactivated under the conditions of light and heating, ensures long-term stable antibacterial, it can be seen that the present application has obvious advantages in antibacterial performance, structure control, cost control and environmental adaptability, and has wide application prospect.
[0085] The above is only the preferred embodiment of the present application, and does not limit the implementation and protection scope of the present application. For those skilled in the art, it should be realized that any equivalent replacement and obvious change made by using the content of the present application should be included in the protection scope of the present application.
Claims
1. A method for preparing an antibacterial hyper-crosslinked porous polymer material, characterized in that: The following steps are involved: Step 1: Under a nitrogen atmosphere, anhydrous ferric chloride, tetramethyltetraphenylcyclotetrasiloxane, and methylal are added to a round-bottom flask containing 1,2-dichloroethane to obtain a reaction mixture; Step 2: heating the reaction mixture under stirring conditions to raise the temperature of the reaction system to 80° C.-90° C. and maintaining the reaction under reflux. After the reaction is completed, heating is stopped to obtain a hyper-crosslinked porous polymer intermediate; Step 3: sequentially subjecting the hyper-crosslinked porous polymer intermediate to cooling, filtering, washing, extraction, and drying to obtain a hyper-crosslinked porous polymer material; Step 4: uniformly dispersing the hyper-crosslinked porous polymer material in ethanol and ultrasonically treating the mixture to form a mixed solution; then adding a silver nitrate solution to the mixed solution at room temperature to carry out a light-shielding reaction at room temperature to obtain an antibacterial hyper-crosslinked porous polymer material intermediate; Step 5: Add sodium borohydride solution to the antibacterial hyper-crosslinked porous polymer intermediate and immediately centrifuge. After centrifugation, retain the bottom precipitate, wash the precipitate several times with ethanol and deionized water, and then freeze-dry to obtain the antibacterial hyper-crosslinked porous polymer.
2. The method for preparing an antibacterial hyper-crosslinked porous polymer material according to claim 1, characterized in that: The molar ratio of the methylal to the tetramethyltetraphenylcyclotetrasiloxane in the reaction mixture is 6 to 12:1, and the molar ratio of the anhydrous ferric chloride to the tetramethyltetraphenylcyclotetrasiloxane is 4 to 5:
1.
3. The method for preparing an antibacterial hyper-crosslinked porous polymer material according to claim 1, characterized in that: In the step 3, the washing treatment is to use an organic solvent to wash several times, the extraction treatment is to use a Soxhlet extractor to extract for 40h-50h, and the drying treatment is to dry in a vacuum oven at 50°C-70°C for 20h-30h.
4. The method for preparing an antibacterial hyper-crosslinked porous polymer material according to claim 1, characterized in that: In the step 4, the molar ratio of the hyper-crosslinked porous polymer material to the silver nitrate solution is 1:10-11.
5. The method for preparing an antibacterial hyper-crosslinked porous polymer material according to claim 1, characterized in that: In the step 5, the amount of the sodium borohydride solution added is 10 mL-20 mL, and the molar concentration of the sodium borohydride solution is 0.5 mol / L-1 mol / L.
6. The method for preparing an antibacterial hyper-crosslinked porous polymer material according to claim 1, characterized in that: The freeze drying process uses a freeze dryer.
7. The method for preparing an antibacterial hyper-crosslinked porous polymer material according to claim 1, characterized in that: The freeze-drying treatment time is 13h-16h.
8. The method for preparing an antibacterial hyper-crosslinked porous polymer material according to claim 1, characterized in that: The molar concentration of the silver nitrate solution is 0.2 mol / L-0.5 mol / L, and the amount of the silver nitrate solution added is 50 mL-60 mL.