CN115819775A - Antibacterial self-repairing polysiloxane elastomer and preparation method thereof - Google Patents

Antibacterial self-repairing polysiloxane elastomer and preparation method thereof Download PDF

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CN115819775A
CN115819775A CN202310145708.5A CN202310145708A CN115819775A CN 115819775 A CN115819775 A CN 115819775A CN 202310145708 A CN202310145708 A CN 202310145708A CN 115819775 A CN115819775 A CN 115819775A
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polysiloxane
repairing
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antibacterial self
elastomer
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CN115819775B (en
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伊港
王文嫔
郑建青
刘海龙
毛正楠
肖楚红
孙晓雷
张帅
周磊
刘瑞湖
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Shandong Dongyue Organic Silicon Material Co Ltd
Qingdao University of Science and Technology
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Shandong Dongyue Organic Silicon Material Co Ltd
Qingdao University of Science and Technology
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Abstract

The invention discloses an antibacterial self-repairing polysiloxane elastomer and a preparation method thereof, belonging to the technical field of polysiloxane elastomers. Firstly, carrying out ring-opening polymerization on tetramethyl tetravinylcyclotetrasiloxane and octamethylcyclotetrasiloxane to obtain polysiloxane with a double bond on a side chain, and then carrying out click chemical reaction on the polysiloxane with the double bond on the side chain, a dicarboxyl monomer and a photoinitiator to obtain dicarboxyl functionalized polysiloxane A; then (3-aminopropyl) terminated poly (dimethyl siloxane) reacts with isocyanate monomer B at normal temperature to obtain polysiloxane B with a main chain containing carbamido; and finally, blending polysiloxane A and polysiloxane B in a solvent, introducing Ag (I) for competitive coordination, casting to form a film, and drying the solvent to obtain the antibacterial self-repairing polysiloxane elastomer. The elastomer prepared by the invention has excellent toughness, self-repairing performance and antibacterial property, and has potential application value in wearable equipment, biomedical materials and other aspects.

Description

Antibacterial self-repairing polysiloxane elastomer and preparation method thereof
Technical Field
The invention relates to the technical field of polysiloxane elastomers, in particular to an antibacterial self-repairing polysiloxane elastomer and a preparation method thereof.
Background
Polysiloxanes are a general term for a class of polymers with a main chain of Si-O, and due to the nature of the Si-O main chain, polysiloxane elastomers have many excellent chemical properties, such as good chemical stability and flexibility. These unique properties also make polysiloxanes important for wearable skin and medical applications. However, the traditional polysiloxane material has poor mechanical property and is easy to damage, and the application range of polysiloxane is seriously influenced.
Compared with the common polysiloxane elastomer, the self-repairing polysiloxane elastomer can be automatically repaired without external stimulation under the condition of external force damage. The self-healing of elastomers is achieved primarily by reversible interactions in the network, such as hydrogen bonding, metal coordination bonds, diels-Alder reactions, dynamic disulfide bonds, and the like. Hydrogen bonding is a weak interaction with directional saturation. Polysiloxane elastomers with multiple hydrogen bonds were synthesized by the Zhang Strength topic group of university of south China (Journal of Applied Polymer Science, 2013, 129, 2435-2442) using multiple acid functional group interactions. Due to the reversibility of hydrogen bonding, elastomers can exhibit self-healing properties at room temperature and even lower temperatures. A coordination bond is formed by one atom independently providing an electron pair, while the other atom provides an empty orbital. Because the content of metal ions and ligand can be adjusted, the mechanical property of the material can be changed.
Multiple-interaction co-operative elastomers tend to exhibit better strength and self-healing properties than single-interaction polysiloxane elastomers.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the preparation method is simple, the polysiloxane elastomer can be self-repaired at low temperature, and the addition of silver ions enables the elastomer to have antibacterial performance and excellent mechanical performance, and the antibacterial self-repairing polysiloxane elastomer has wide application value in the fields of wearable equipment and medicines.
In order to achieve the purpose, in one aspect, the invention provides a preparation method of an antibacterial self-repairing polysiloxane elastomer, which adopts a mode of blending two kinds of functional polysiloxanes, and then Ag (I) is added for competitive coordination. Specifically, polysiloxane with a dicarboxyl group on a side chain and polysiloxane with a carbamido group on a main chain are blended, a weak hydrogen bond effect is constructed in a polymer network, and then an Ag (I) compound is added to form a strong competitive coordination effect of Ag (I) with the dicarboxyl group and the carbamido group, so that the antibacterial self-repairing polysiloxane elastomer is obtained.
Preferably, the method specifically comprises the following steps:
preparation of polysiloxane containing double bonds in the side chain of S1: mixing tetramethyltetravinylcyclotetrasiloxane (V4) and octamethylcyclotetrasiloxane (D4), adding a phosphazene base catalyst dissolved in toluene and a tetramethyldivinylsiloxane end-capping reagent, uniformly mixing, carrying out polymerization reaction, settling in methanol or petroleum ether, washing, and drying to obtain polysiloxane with a side chain containing double bonds;
preparation of S2 polysiloxane A containing dicarboxy in side chain: dissolving the product obtained in the step S1 in a solvent, adding a photoinitiator and a dicarboxylic acid monomer, and reacting at room temperature N 2 Or ultraviolet light induced click chemistry reaction under the protection of inert gasSettling and washing with deionized water to remove unreacted monomers to obtain polysiloxane A with a side chain containing dicarboxyl;
preparation of S3 polysiloxane B containing ureido groups in the backbone: dissolving bis (3-aminopropyl) terminated poly (dimethyl siloxane), isocyanate monomer B and triethylamine catalyst into a solvent, and reacting at 0-10 ℃ in an environment with N 2 Or under the protection of inert gas, uniformly mixing, continuously stirring for reaction to obtain viscous liquid, washing with methanol, and precipitating to obtain polysiloxane B with a main chain containing carbamido;
s4, preparation of the antibacterial self-repairing polysiloxane elastomer: dissolving the polysiloxane A prepared in the step S2 and the polysiloxane B prepared in the step S3 in tetrahydrofuran, dropwise adding a tetrahydrofuran solution of silver trifluoromethanesulfonate, and adding the solution in N 2 Or under the protection of inert gas, reacting in a dark place, pouring the reacted solution into a mold, and drying the solvent to obtain the antibacterial self-repairing polysiloxane elastomer.
Preferably, in step S1, the phosphazene base catalyst is a phosphazene ligand P2-tert-butyl or phosphazene ligand P4-tert-octyl; the polymerization reaction temperature is 25-40 deg.C, and the time is 20-50min.
Preferably, in the step S1, the molar ratio of the tetramethyltetravinylcyclotetrasiloxane to the octamethylcyclotetrasiloxane is 1 (5-7); the dosage of the phosphazene base catalyst is 0.05-0.2% of the mass sum of the tetramethyltetravinylcyclotetrasiloxane and the octamethylcyclotetrasiloxane; the amount of the end-capping agent is 0.1 to 0.3 percent of the mass sum of the tetramethyltetravinylcyclotetrasiloxane and the octamethylcyclotetrasiloxane; the dosage of the toluene is 2-4% of the total mass of the tetramethyltetravinylcyclotetrasiloxane and the octamethylcyclotetrasiloxane.
Preferably, in step S2, the dicarboxylic acid monomer is mercaptosuccinic acid or 2, 3-dimercaptosuccinic acid; the photoinitiator is 2, 2-dimethoxy-phenylacetophenone, the solvent is dichloromethane, trichloromethane or tetrahydrofuran, and the dosage of the solvent is 5-10 times of the mass of the added polysiloxane with the side chain containing double bonds.
Preferably, in step S2, the molar ratio of the dicarboxylic acid monomer to the vinyl group in the polysiloxane having a double bond in the side chain added is (2-3): 1.
Preferably, in step S3, the isocyanate monomer B is toluene-2, 5-diisocyanate, p-phenylene diisocyanate or m-xylylene diisocyanate; the solvent is dichloromethane, trichloromethane or tetrahydrofuran, and the amount of the solvent is 1-5 times of the mass of the bis (3-aminopropyl) terminated poly (dimethyl siloxane).
Preferably, in step S3, the molar ratio of the bis (3-aminopropyl) terminated poly (dimethylsiloxane) to the isocyanate monomer B is 1 (1-1.3); the dosage of the triethylamine catalyst is 0.1-0.2% of the mass of the bis (3-aminopropyl) terminated poly (dimethyl siloxane).
Preferably, in step S4, the amount of silver trifluoromethanesulfonate added is 25 to 35% of the total mass of polysiloxane A and polysiloxane B.
On the other hand, the invention also provides the antibacterial self-repairing polysiloxane elastomer prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention designs an antibacterial self-repairing polysiloxane elastomer based on Ag (I) coordination and hydrogen bond action, hydrogen bonds can be formed between carbamido groups or dicarboxyl groups, and the elastomer has good toughness due to the rapid fracture and recombination of the hydrogen bonds under the condition of external force; the addition of Ag (I) introduces the competitive coordination bond action with the dicarboxyl and the carbamido, and enhances the strength of the elastomer.
2. According to the antibacterial self-repairing polysiloxane elastomer based on the coordination and hydrogen bond action of Ag (I), the competitive coordination and hydrogen bond action of Ag (I), dicarboxyl and ureido are designed in a polymer network, wherein the hydrogen bond and the coordination bond of Ag (I) are reversible bonds, and self-repairing can be performed at low temperature after breakage, and the polysiloxane elastomer is endowed with good antibacterial performance due to the existence of silver ions, so that the prepared elastomer has excellent toughness, self-repairing performance and antibacterial property, is simple in reaction step, suitable for large-scale production and has great potential value in the field of antibacterial materials.
Drawings
FIG. 1 is a graph showing the mechanical properties of an antibacterial self-repairing polysiloxane elastomer obtained in examples 1 to 3, based on the coordination and hydrogen bonding of Ag (I).
FIG. 2 is a bar chart of the antibacterial performance test of the antibacterial self-repairing polysiloxane elastomer based on Ag (I) coordination and hydrogen bonding obtained in example 2.
FIG. 3 is a photograph showing comparison between before and after self-healing of an antimicrobial self-healing polysiloxane elastomer based on coordination and hydrogen bonding of Ag (I) obtained in example 3.
Detailed Description
The present invention will be specifically described in the following examples, but the present invention is not limited to these examples.
The raw materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1
The preparation method of the antibacterial self-repairing polysiloxane elastomer comprises the following steps:
preparation of polysiloxane containing double bonds in the side chain of S1: 5.2g of tetramethyltetravinylcyclotetrasiloxane (V4) and 25.2g of octamethylcyclotetrasiloxane (D4) were weighed out in N 2 Uniformly mixing under the condition, dissolving 0.03g of phosphazene ligand P2-tert-butyl in 1mL of toluene, adding the solution into the solution, adding 0.06g of tetramethyldivinylsiloxane end-capping agent, uniformly mixing, stirring for 30min at 30 ℃ for carrying out polymerization reaction, dropping sufficient methanol after the reaction for settling, washing and drying, and repeating for three times to obtain polysiloxane with a side chain containing double bonds;
preparation of S2 polysiloxane A containing dicarboxy in side chain: 2.4g of the polysiloxane having a double bond in the side chain prepared in step S1 were weighed out and dissolved in 13mL of tetrahydrofuran under N 2 Under protection, adding 25mg of photoinitiator 2, 2-dimethoxy-phenylacetophenone and 0.44g of mercaptosuccinic acid into the solution, uniformly mixing, under the condition of room temperature, inducing click chemical reaction for 30min by illumination of an ultraviolet lamp, then pouring the polymer into deionized water, settling and washing, repeating for three times, removing unreacted monomers, and carrying out vacuum drying to obtain polysiloxane A with a side chain containing dicarboxyl;
preparation of S3 polysiloxane B containing carbamido in main chainPreparing: 8g of bis (3-aminopropyl) blocked poly (dimethylsiloxane), 0.5g of m-xylylene diisocyanate and 0.016g of triethylamine catalyst were dissolved in 16mL of chloroform at 0 ℃ under N 2 Continuously stirring for reaction for four days under protection to obtain viscous liquid, washing with methanol, and precipitating to obtain polysiloxane B with ureido-containing main chain;
s4, preparation of the antibacterial self-repairing polysiloxane elastomer: 0.7g of polysiloxane A having a biscarboxyl group in the side chain prepared in step S2 and 16.3g of polysiloxane B having a ureido group in the main chain prepared in step S3 were dissolved in 15mL of tetrahydrofuran, and 4.25g of a tetrahydrofuran solution of silver trifluoromethanesulfonate (silver trifluoromethanesulfonate dissolved in 3mL of tetrahydrofuran) was added dropwise over N 2 Reacting for 24 hours at room temperature in a dark place under protection; and pouring the reacted solution into a polytetrafluoroethylene mold, and drying the solvent to obtain the antibacterial self-repairing polysiloxane elastomer, wherein the strength of the elastomer is 1.8MPa, and the elongation at break is 516% (shown in figure 1).
Example 2
The preparation method of the antibacterial self-repairing polysiloxane elastomer comprises the following steps:
preparation of polysiloxane containing double bonds in the side chain of S1: weighing 5.2g of tetramethyltetravinylcyclotetrasiloxane (V4) and 22.4g of octamethylcyclotetrasiloxane (D4), uniformly mixing under the protection of argon, dissolving 0.014g of phosphazene ligand P4-tert-octyl in 0.6mL of toluene, adding into the solution, adding 0.03g of tetramethyldivinylsiloxane end-capping agent, uniformly mixing, stirring at 25 ℃ for 50min for carrying out polymerization reaction, dropping sufficient petroleum ether after the reaction, settling, washing and drying, and repeating for three times to obtain polysiloxane with a side chain containing double bonds;
preparation of S2 polysiloxane A containing dicarboxy in side chain: weighing 2.4g of polysiloxane with a double bond on a side chain prepared in the step S1, dissolving the polysiloxane in 16mL of trichloromethane, adding 25mg of photoinitiator 2, 2-dimethoxy-phenylacetophenone and 0.4g of mercaptosuccinic acid into the solution under the protection of argon gas, uniformly mixing, inducing click chemical reaction for 30min under the condition of room temperature by ultraviolet lamp illumination, then pouring the polymer into deionized water for settling and washing, repeating for three times, removing unreacted monomers, and performing vacuum drying to obtain polysiloxane A with a dicarboxyl on a side chain;
preparation of S3 polysiloxane B containing ureido groups in the backbone: dissolving 8g of bis (3-aminopropyl) terminated poly (dimethyl siloxane), 0.55g of p-phenylene diisocyanate and 0.008g of triethylamine catalyst in 9mL of tetrahydrofuran, continuously stirring and reacting for four days at 5 ℃ under the protection of argon to obtain viscous liquid, washing with methanol, and precipitating to obtain polysiloxane B with a ureido-containing main chain;
s4, preparation of the antibacterial self-repairing polysiloxane elastomer: dissolving 1g of polysiloxane A with a dicarboxyl group on a side chain prepared in the step S2 and 16.3g of polysiloxane B with a carbamido group on a main chain prepared in the step S3 in 17mL of tetrahydrofuran, dropwise adding 6.1g of tetrahydrofuran solution of silver trifluoromethanesulfonate (the silver trifluoromethanesulfonate is dissolved in 3mL of tetrahydrofuran), and reacting at room temperature in a dark place for 24 hours under the protection of argon; and pouring the reacted solution into a polytetrafluoroethylene mold, and drying the solvent to obtain the antibacterial self-repairing polysiloxane elastomer, wherein the strength of the elastomer is 1.9MPa, and the elongation at break is 715 percent (shown in figure 1). Meanwhile, as can be seen from fig. 2, the antibacterial rate of the antibacterial self-repairing polysiloxane elastomer prepared in example 2 to staphylococcus aureus and escherichia coli is about 82% and 85%.
Example 3
The preparation method of the antibacterial self-repairing polysiloxane elastomer comprises the following steps:
preparation of polysiloxane having double bonds in the S1 side chain: 5.2g of tetramethyltetravinylcyclotetrasiloxane (V4) and 31.3g of octamethylcyclotetrasiloxane (D4) were weighed out in N 2 Uniformly mixing under the condition, dissolving 0.07g of phosphazene ligand P2-tert-butyl in 1.7mL of toluene, adding the solution into the solution, adding 0.1g of tetramethyldivinylsiloxane end-capping agent, stirring for 20min at 40 ℃ for polymerization reaction, dropping sufficient methanol after the reaction for settlement, washing and drying, and repeating the steps for three times to obtain polysiloxane with a side chain containing double bonds;
preparation of S2 polysiloxane A containing dicarboxy in side chain: 2.4g of the polysiloxane having double bonds in the side chains prepared in step S1 are weighed out and mixedDissolved in 14mL of dichloromethane in N 2 Under protection, adding 25mg of photoinitiator 2, 2-dimethoxy-phenylacetophenone and 0.8g of 2, 3-dimercaptosuccinic acid into the solution, uniformly mixing, inducing click chemical reaction for 30min under room temperature conditions by ultraviolet lamp illumination, then pouring the polymer into deionized water for settling and washing, repeating for three times, removing unreacted monomers, and drying in vacuum to obtain polysiloxane A with a side chain containing dicarboxyl;
preparation of S3 polysiloxane B containing ureido groups in the backbone: 8g of bis (3-aminopropyl) terminated poly (dimethylsiloxane) was dissolved in 30mL of methylene chloride with 0.56g of toluene-2, 5-diisocyanate and 0.012g of triethylamine catalyst at 10 ℃ in N 2 Continuously stirring for reaction for four days under protection to obtain viscous liquid, washing with methanol, and precipitating to obtain polysiloxane B with ureido-containing main chain;
s4, preparation of the antibacterial self-repairing polysiloxane elastomer: 1.3g of polysiloxane A having a biscarboxyl group in the side chain prepared in step S2 and 16.3g of polysiloxane B having a ureido group in the main chain prepared in step S3 were dissolved in 17mL of tetrahydrofuran, and 5.3g of a tetrahydrofuran solution of silver trifluoromethanesulfonate (silver trifluoromethanesulfonate dissolved in 3mL of tetrahydrofuran) was added dropwise to the solution in N 2 Reacting for 24 hours at room temperature in a dark place under protection; and pouring the reacted solution into a polytetrafluoroethylene mold, and drying the solvent to obtain the antibacterial self-repairing polysiloxane elastomer, wherein the strength of the elastomer is 1.8MPa, and the elongation at break is 922% (as shown in figure 1). Meanwhile, as can be seen from fig. 3, after the antibacterial self-repairing polysiloxane elastomer prepared in example 3 is self-repaired for 24 hours at room temperature, the section of the antibacterial self-repairing polysiloxane elastomer is visually observed to be healed, which indicates that the polysiloxane elastomer actually has self-repairing capability.

Claims (10)

1. The preparation method of the antibacterial self-repairing polysiloxane elastomer is characterized in that polysiloxane with a dicarboxyl group on a side chain and polysiloxane with a carbamido group on a main chain are blended, and then an Ag (I) compound is added for competitive coordination, so that the antibacterial self-repairing polysiloxane elastomer is obtained.
2. The method of preparing the antibacterial self-healing polysiloxane elastomer of claim 1, comprising the steps of:
preparation of polysiloxane containing double bonds in the side chain of S1: mixing tetramethyltetravinylcyclotetrasiloxane and octamethylcyclotetrasiloxane, adding a phosphazene base catalyst dissolved in toluene and a tetramethyldivinylsiloxane end-capping reagent, uniformly mixing, carrying out polymerization reaction, settling in methanol or petroleum ether, washing, and drying to obtain polysiloxane with a side chain containing double bonds;
preparation of S2 polysiloxane A containing dicarboxy in side chain: dissolving the product obtained in the step S1 in a solvent, adding a photoinitiator and a dicarboxylic acid monomer, and reacting at room temperature N 2 Or under the protection of inert gas, ultraviolet light induces click chemical reaction, deionized water is used for settling and washing, and unreacted monomers are removed to obtain polysiloxane A with side chains containing dicarboxyl;
preparation of S3 polysiloxane B containing ureido groups in the backbone: dissolving bis (3-aminopropyl) terminated poly (dimethyl siloxane), isocyanate monomer B and triethylamine catalyst into a solvent, and reacting at 0-10 ℃ in an environment with N 2 Or under the protection of inert gas, uniformly mixing, continuously stirring for reaction to obtain viscous liquid, washing with methanol, and precipitating to obtain polysiloxane B with a main chain containing carbamido;
s4, preparation of the antibacterial self-repairing polysiloxane elastomer: dissolving the polysiloxane A prepared in the step S2 and the polysiloxane B prepared in the step S3 in tetrahydrofuran, dropwise adding a tetrahydrofuran solution of silver trifluoromethanesulfonate, and adding the solution in N 2 Or under the protection of inert gas, reacting in a dark place, pouring the reacted solution into a mold, and drying the solvent to obtain the antibacterial self-repairing polysiloxane elastomer.
3. The preparation method of the antibacterial self-repairing polysiloxane elastomer as claimed in claim 2, wherein in step S1, the phosphazene base catalyst is a phosphazene ligand P2-tert-butyl group or a phosphazene ligand P4-tert-octyl group; the polymerization reaction temperature is 25-40 deg.C, and the time is 20-50min.
4. The preparation method of the antibacterial self-repairing polysiloxane elastomer according to claim 2, wherein in the step S1, the molar ratio of the tetramethyltetravinylcyclotetrasiloxane to the octamethylcyclotetrasiloxane is 1 (5-7); the dosage of the phosphazene base catalyst is 0.05-0.2% of the mass sum of the tetramethyltetravinylcyclotetrasiloxane and the octamethylcyclotetrasiloxane; the amount of the end-capping agent is 0.1 to 0.3 percent of the mass sum of the tetramethyltetravinylcyclotetrasiloxane and the octamethylcyclotetrasiloxane; the dosage of the toluene is 2-4% of the total mass of the tetramethyltetravinylcyclotetrasiloxane and the octamethylcyclotetrasiloxane.
5. The method for preparing the antibacterial self-repairing polysiloxane elastomer according to claim 2, wherein in step S2, the dicarboxylic acid monomer is mercaptosuccinic acid or 2, 3-dimercaptosuccinic acid; the photoinitiator is 2, 2-dimethoxy-phenylacetophenone, the solvent is dichloromethane, trichloromethane or tetrahydrofuran, and the dosage of the solvent is 5-10 times of the mass of the added polysiloxane with the side chain containing double bonds.
6. The method for preparing the antibacterial self-repairing polysiloxane elastomer according to claim 2, wherein in the step S2, the molar ratio of the dicarboxylic acid monomer to the vinyl group in the polysiloxane with the double bond in the side chain is (2-3): 1.
7. The method for preparing the antibacterial self-repairing polysiloxane elastomer according to claim 2, wherein in step S3, the isocyanate monomer B is toluene-2, 5-diisocyanate, p-phenylene diisocyanate or m-xylylene diisocyanate; the solvent is dichloromethane, trichloromethane or tetrahydrofuran, and the amount of the solvent is 1-5 times of the mass of the bis (3-aminopropyl) terminated poly (dimethyl siloxane).
8. The preparation method of the antibacterial self-repairing polysiloxane elastomer according to claim 2, wherein in step S3, the molar ratio of the bis (3-aminopropyl) terminated poly (dimethylsiloxane) to the isocyanate monomer B is 1 (1-1.3); the dosage of the triethylamine catalyst is 0.1-0.2% of the mass of the bis (3-aminopropyl) terminated poly (dimethyl siloxane).
9. The method for preparing the antibacterial self-repairing polysiloxane elastomer according to claim 2, wherein in the step S4, the addition amount of the silver trifluoromethanesulfonate is 25-35% of the total mass of the polysiloxane A and the polysiloxane B.
10. The antibacterial self-repairing polysiloxane elastomer prepared by the preparation method of any one of claims 1-9.
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