Polymer network hybrid material containing disulfide bonds and ether bonds as well as preparation method and application of polymer network hybrid material

Abstract

The invention belongs to the field of synthesis and preparation of high polymer materials, and relates to a polymer network hybrid material containing disulfide bonds and ether bonds as well as a preparation method and application of the polymer network hybrid material. The polymer network hybrid material is composed of a polydisulfide chain segment, a polyether chain segment and coordination metal ions, a polydisulfide chain segment and a polyether chain segment are connected through a carboxylic ester covalent bond to form a covalent cross-linked network, and part of lateral carboxyl groups of the polydisulfide chain segment and coordination metal ions form a dynamic coordination cross-linked network through coordination bonds. According to the polymer network hybrid material containing the disulfide bond and the ether bond, the network structure is jointly constructed by a hydrogen bond, a metal ion coordination bond and a stable ester group donor bond, and a polydisulfide compound chain segment containing a high disulfide bond content and a hydrophilic carboxyl side group and a hydrophobic polytetrahydrofuran chain segment with good flexibility are organically combined; the material is endowed with excellent antibacterial performance and self-repairing performance.

Description

Technical Field

[0001] The invention belongs to the field of polymer material synthesis and preparation, and in particular relates to a polymer network hybrid material containing disulfide bonds and ether bonds, and a preparation method and application thereof. Background Art

[0002] Polydisulfide compounds are functional polymers with rich disulfide bonds in the main chain. The enriched disulfide bonds on the main chain give the material excellent dynamic properties and stimulus response characteristics, and can be used in advanced fields such as sensing materials, antibacterial coatings, and drug-carrying materials. The polymer of 1,2-dithiolane-3-octanoic acid, also known as polythioic acid, is a typical example of polydisulfide compounds. It is prepared from 1,2-dithiolane-3-octanoic acid monomers through ring-opening polymerization. It has a fatty main chain structure rich in disulfide bonds and a large number of carboxyl side group structures, showing excellent self-healing and adhesion properties. See: J.Am.Chem.Soc.2022,144,2022-2033; Sci.Adv,2018,4:eaat8192. Polylipoic acid or its derivatives have application value in multiple fields such as biomedical patches, gel patches, antibacterial materials, etc., see CN202210305032, CN202210496117 and CN201811248965.

[0003] Polyether materials are a type of polymer material rich in CO ether bonds in the main chain, including polyethylene glycol, polyethylene oxide, polypropylene oxide, polytetrahydrofuran and many other polymers. They have good biocompatibility and durability and are used in fields such as biomedical materials.

[0004] In the prior art, there has been no public report on the formation of copolymer materials by chemically combining polydisulfide compounds and polyethers, nor has there been any public report on the in-situ formation of hybrid materials by bonding polydisulfide compounds, polyethers and metal ions. Summary of the invention

[0005] The purpose of the present invention is to solve the above-mentioned problems existing in the prior art and to provide a polymer network hybrid material containing disulfide bonds and ether bonds and a preparation method thereof. The material exhibits excellent antibacterial properties and self-healing properties, and the preparation method of the present invention is simple and controllable, can effectively adjust the copolymer composition and crosslinking density of the copolymer network, and effectively regulate and improve the performance of the polymer, and has good application prospects.

[0006] In order to achieve the above-mentioned object, the first aspect of the present invention provides a polymer network hybrid material containing disulfide bonds and ether bonds, wherein the polymer network hybrid material is composed of a polydisulfide compound segment, a polyether segment and a coordinated metal ion;

[0007] The polydisulfide chain segments and the polyether chain segments are connected via carboxylate covalent bonds to form a covalent cross-linked network, and some side carboxyl groups of the polydisulfide chain segments and the coordinated metal ions form a dynamic coordinated cross-linked network via coordination bonds.

[0008] The second aspect of the present invention provides a method for preparing the polymer network hybrid material containing disulfide bonds and ether bonds, comprising the following steps:

[0009] (1) Synthesis of ester-functionalized polyethers containing 1,2-disulfide five-membered ring structural units at both ends

[0010] Under nitrogen protection and stirring conditions, a double-terminal hydroxyl functionalized polyether compound and a 1,2-disulfide five-membered ring compound are subjected to an esterification reaction in a first organic solvent system containing a proton transfer agent and a dehydrating agent to obtain a double-terminal ester functionalized polyether containing a 1,2-disulfide five-membered ring structural unit;

[0011] (2) Synthesis of polymer networks containing disulfide bonds and ether bonds

[0012] Under nitrogen protection, the double-terminal ester-functionalized polyether containing 1,2-disulfide five-membered ring structural units synthesized in step (1) is used as a macromonomer, and a 1,2-disulfide five-membered ring compound is subjected to a cationic copolymerization reaction in a second organic solvent system containing an initiator system to form a cross-linked network in which polydisulfide compound segments and polyether segments are connected by carboxylate covalent bonds; the initiator system is composed of an initiator, a metal-based co-initiator, and an optional oxygen-containing organic compound;

[0013] (3) Synthesis of polymer network hybrid materials containing disulfide bonds and ether bonds

[0014] After the copolymerization reaction is completed, a terminator is added to terminate the polymerization reaction, and the metal ions in the chain end counterions derived from the metal-based co-initiator are released and coordinated with part of the side carboxyl groups of the polydisulfide compound segments in the above-mentioned polymer network containing disulfide bonds and ether bonds, thereby in situ preparing the polymer network hybrid material containing disulfide bonds and ether bonds.

[0015] The third aspect of the present invention provides the use of the polymer network hybrid material containing disulfide bonds and ether bonds or the polymer network hybrid material containing disulfide bonds and ether bonds obtained by the preparation method in the field of biological protective films.

[0016] The present invention has the following effects:

[0017] (1) The polymer network hybrid material containing disulfide bonds and ether bonds provided by the present invention has the structural characteristics of a block / graft copolymer network, and its network structure is jointly constructed by hydrogen bonds, metal ion coordination bonds and stable covalent bonds, and has multiple responsiveness.

[0018] (2) The composition of the three structural elements A, B, and C in the polymer network hybrid material provided by the present invention can be regulated by specific implementation steps of controlled polymerization to achieve controlled synthesis of designed structure polymers.

[0019] (3) The present invention imparts excellent physical and chemical properties such as amphiphilicity, chemical stability, and biocompatibility to the material through the organic combination of a polydisulfide compound segment containing a high disulfide bond content and a hydrophilic side group and a hydrophobic polytetrahydrofuran segment with good flexibility, thereby providing a good basis for the use of the material.

[0020] (4) The polymer network hybrid material provided by the present invention has excellent antibacterial and self-healing properties and has broad application prospects.

[0021] Other features and advantages of the present invention will be described in detail in the following detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] The above and other objects, features and advantages of the present invention will become more apparent through a more detailed description of exemplary embodiments of the present invention in conjunction with the accompanying drawings, wherein like reference numerals generally represent like components throughout the exemplary embodiments of the present invention.

[0023] Figure 1 The diagram shows the antibacterial effect of Escherichia coli (E. coli.) and Staphylococcus aureus (S. aureus) according to an embodiment of the present invention. DETAILED DESCRIPTION

[0024] The preferred embodiments of the present invention will be described in more detail below. Although the preferred embodiments of the present invention are described below, it should be understood that the present invention can be implemented in various forms and should not be limited to the embodiments set forth herein.

[0025] In order to achieve the above-mentioned object, the first aspect of the present invention provides a polymer network hybrid material containing disulfide bonds and ether bonds, wherein the polymer network hybrid material is composed of a polydisulfide compound segment, a polyether segment and a coordinated metal ion;

[0026] The polydisulfide chain segments and the polyether chain segments are connected via carboxylate covalent bonds to form a covalent cross-linked network, and some side carboxyl groups of the polydisulfide chain segments and the coordinated metal ions form a dynamic coordinated cross-linked network via coordination bonds.

[0027] According to the present invention, preferably, based on the total mass of the polydisulfide compound segment and the polyether segment, the mass content of the polyether segment is 4-30%, preferably 5-25%, and more preferably 6-22%; the mass content of the coordinated metal ion is 0.3-2.0% of the polydisulfide compound segment, preferably 0.4-1.8%, and more preferably 0.5-1.6%.

[0028] According to the present invention, preferably, the polydisulfide compound is a compound containing structural units derived from a 1,2-disulfide five-membered ring compound and the structural units are connected by chemical bonds; the 1,2-disulfide five-membered ring compound is selected from at least one of 1,2-dithiolane-3-butyric acid, 1,2-dithiolane-3-hexanoic acid, 1,2-dithiolane-3-octanoic acid, 1,2-dithiolane-3-nonanoic acid, 1,2-dithiolane-4-carboxylic acid, 1,2-dithiolane-4-hydroxy-3-octanoic acid, 1,2-dithiolane-4-hydroxy-3-pentanoic acid, 1,2-dithiolane-4-hydroxy-3-butyric acid and 1,2-dithiolane-4-carbonyl-3-hexanoic acid.

[0029] According to the present invention, preferably, the polyether segment is at least one of a polyethylene oxide segment, a polyethylene glycol segment, a polypropylene oxide segment and a polytetrahydrofuran segment.

[0030] According to the present invention, preferably, the coordinating metal ion is selected from Ti 4+ Sn 4+ , Fe 3+ and Al 3+ At least one of .

[0031] The second aspect of the present invention provides a method for preparing the polymer network hybrid material containing disulfide bonds and ether bonds, comprising the following steps:

[0032] (1) Synthesis of ester-functionalized polyethers containing 1,2-disulfide five-membered ring structural units at both ends

[0033] Under nitrogen protection and stirring conditions, a double-terminal hydroxyl functionalized polyether compound and a 1,2-disulfide five-membered ring compound are subjected to an esterification reaction in a first organic solvent system containing a proton transfer agent and a dehydrating agent, and then washed and separated and washed with water until the aqueous phase is neutral, and then dried and purified by reduced pressure distillation to obtain a double-terminal ester functionalized polyether containing a 1,2-disulfide five-membered ring structural unit;

[0034] (2) Synthesis of polymer networks containing disulfide bonds and ether bonds

[0035] Under nitrogen protection, the double-terminal ester-functionalized polyether containing 1,2-disulfide five-membered ring structural units synthesized in step (1) is used as a macromonomer, and a 1,2-disulfide five-membered ring compound is copolymerized in a second organic solvent system containing an initiator system to form a cross-linked network in which polydisulfide compound segments and polyether segments are connected by carboxylate covalent bonds; the initiator system is composed of an initiator, a metal-based co-initiator, and an optional oxygen-containing organic compound;

[0036] (3) Synthesis of polymer network hybrid materials containing disulfide bonds and ether bonds

[0037] After the copolymerization reaction is completed, a terminator is added to terminate the polymerization reaction, and the metal ions in the chain end counterions derived from the metal-based co-initiator are released and coordinated with part of the side carboxyl groups of the polydisulfide compound segments in the above-mentioned polymer network containing disulfide bonds and ether bonds, thereby in situ preparing the polymer network hybrid material containing disulfide bonds and ether bonds.

[0038] According to a specific embodiment of the present invention, after the reaction is completed, the polymerization system solution is injected into a glass culture dish or PTFE mold of a certain size, and a transparent polymer film can be obtained after volatilization at room temperature for 5 minutes to 14 days. Preferably, the volatilization time at room temperature is 7 days; the polymerization system solution can also be directly made into a film through a continuous casting process. Increasing the temperature or under a certain vacuum condition is conducive to the volatilization of the solvent and can shorten the solvent volatilization time.

[0039] According to the present invention, preferably, in step (1), the dehydrating agent is a carbodiimide compound, preferably selected from at least one of N,N'-dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide, 1-ethyl-(3-dimethylaminopropyl)carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide and their hydrochlorides, more preferably N,N'-dicyclohexylcarbodiimide and / or N,N'-diisopropylcarbodiimide hydrochloride.

[0040] According to the present invention, preferably, the proton transfer agent is a compound containing pyridine and / or a tertiary amine structure, preferably selected from at least one of trimethylamine, triethylamine, triphenylamine, pyridine, 4-aminopyridine, 4-(N,N-dimethyl)pyridine and 4-(N,N-diethyl)pyridine, more preferably selected from at least one of triethylamine, triphenylamine and 4-(N,N-dimethyl)pyridine.

[0041] According to the present invention, preferably, the first organic solvent is selected from at least one of dichloromethane, chloroform, dichloroethane, tetrahydrofuran, N,N-dimethylformamide and dimethyl sulfoxide.

[0042] According to the present invention, preferably, in step (1), the molar ratio of the double-terminal hydroxyl functionalized polyether to the 1,2-disulfide five-membered ring compound is 1:2.0 to 1:2.5.

[0043] According to the present invention, preferably, the molar ratio of the proton transfer agent to the 1,2-disulfide five-membered ring compound is preferably 1.0 to 1.1.

[0044] According to the present invention, preferably, the molar ratio of the dehydrating agent to the 1,2-disulfide five-membered ring compound is 1.0 to 1.1.

[0045] According to the present invention, preferably, the conditions of the esterification reaction include: reaction temperature of -30 to 30°C, preferably -20 to 25°C, and reaction time of 2 to 24 hours, preferably 12 to 24 hours.

[0046] According to the present invention, preferably, in step (2), the initiator is a monofunctional initiator or a bifunctional initiator, preferably at least one selected from tert-butyl chloride, cumyl chloride, p-dicumyl chloride, benzyl chloride, allyl chloride, benzyl bromide and allyl bromide.

[0047] According to the present invention, preferably, the metal-based co-initiator is a Lewis acid, preferably at least one selected from ferric chloride, titanium tetrachloride, tin tetrachloride, aluminum chloride, ethylaluminum dichloride, isobutylaluminum dichloride, ethylaluminum sesquichloride and isobutylaluminum sesquichloride.

[0048] The oxygen-containing organic compound is selected from at least one of isocarbinol, ethanol, n-propanol, isopropanol, isobutanol, tert-butanol, isopentanol, hexanol, 2-ethylhexanol, ethyl ether, propyl ether, isopropyl ether, methyl tert-butyl ether, n-butyl ether and isobutyl ether.

[0049] According to the present invention, preferably, the second organic solvent is a hydrocarbon and / or a halogenated hydrocarbon, preferably selected from at least one of pentane, cyclopentane, methylcyclopentane, hexane, methylcyclohexane, heptane, octane, methyl chloride, dichloromethane, ethylene dichloride, chloroform, ethyl chloride, dichloroethane, trichloroethane and carbon tetrachloride, more preferably selected from at least one of pentane, hexane, cyclohexane, methylcyclopentane, methylcyclohexane, heptane, octane, ethyl chloride, dichloromethane and dichloroethane.

[0050] According to the present invention, preferably, in step (2), the molar ratio of the 1,2-disulfide five-membered ring compound to the double-end 1,2-disulfide five-membered ring ester functionalized polyether is 25-90, preferably 30-75.

[0051] According to the present invention, preferably, the molar ratio of the initiator to the 1,2-disulfide five-membered ring in the reaction system is 0.020-0.075, preferably 0.025-0.060; the molar ratio of the metal-based co-initiator to the 1,2-disulfide five-membered ring is 0.015-0.085, preferably 0.020-0.075.

[0052] According to the present invention, preferably, the conditions of the cationic copolymerization reaction include: reaction temperature of -35 to 50°C, preferably -25 to 40°C, more preferably -15 to 30°C, reaction time of 1 to 60 min, preferably 1 to 20 min.

[0053] The third aspect of the present invention provides the use of the polymer network hybrid material containing disulfide bonds and ether bonds or the polymer network hybrid material containing disulfide bonds and ether bonds obtained by the preparation method in the field of biological protective films.

[0054] Example 1

[0055] Under high-purity nitrogen protection and stirring, 4.12 g of 1,2-dithiolane-3-octanoic acid (α-lipoic acid, TA), 50 mL of dichloromethane, 2.5 g of 4-(N,N-dimethyl)pyridine (DMAP) and 4 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDCl) were added into the reactor and mixed evenly to form a TA mixed solution; 10 g of double-terminal hydroxyl functionalized polytetrahydrofuran (M n =1000g / mol,PTHF 1k ) and 50mL of dichloromethane were added to the above TA mixed solution and reacted at 0°C for 24h; in the reaction system, TA and PTHF 1k The molar ratio of DMAP to TA is 2.0, the molar ratio of EDCl to TA is 1.02, and the molar ratio of EDCl to TA is 1.04. Hydrochloric acid is added to the reaction system until it is weakly acidic, then washed with sodium bicarbonate solution, and then washed with deionized water until it is neutral. The washed solution is dried with anhydrous calcium chloride for 24 hours and distilled under reduced pressure to obtain polytetrahydrofuran functionalized with lipoic acid ester groups at both ends, namely TA-PTHF. 1k -TA.

[0056] At 0°C and under the protection of high-purity nitrogen, add 10g TA and 1g of the above TA-PTHF into the reactor. 1k -TA and 50mL of dichloromethane were mixed evenly to form a monomer solution; an initiator system containing tert-butyl chloride, isopropanol and FeCl3 was added to the solution to initiate the reaction of TA and TA-PTHF. 1k-TA was subjected to cationic ring-opening copolymerization. Among them, the molar ratio of tert-butyl chloride to TA was 0.027, the molar ratio of isopropanol to TA was 0.031, the molar ratio of FeCl3 to TA was 0.022, and the molar ratio of TA to TA-PTHF was 0.031. 1k -TA molar ratio is 68.5. After 50 minutes of polymerization, 5 mL of ethanol is added to terminate the polymerization reaction. The polymer solution is placed in a glass culture dish and placed on a horizontal plane. It is allowed to stand at 25°C for 1 week to obtain a polymer network film hybrid material. The yield of the polymer material is 99.7%. In the polymer hybrid material, based on the total mass of the 1,2-dithiolane-3-octanoic acid segment and the polyether segment, the mass content of the polyether segment is 6.44%; the mass content of the coordinated iron ion is 0.58% of the poly-1,2-dithiolane-3-octanoic acid segment.

[0057] The polymer network hybrid material has an antibacterial rate of 2.43 against Escherichia coli (E. coli.) and an antibacterial rate of 2.65 against Staphylococcus aureus (S. aureus), and is an excellent intrinsic antibacterial material; scratches on the surface of the polymer network hybrid material film quickly self-heal within 30 minutes at 45°C.

[0058] Example 2

[0059] The polymerization method and post-treatment method are the same as in Example 1, except that: TA-PTHF 1k -TA (same as in Example 1) was added in an amount of 1.5 g, TA and TA-PTHF 1k The molar ratio of -TA is 45.7. The yield of the polymer network hybrid material is 99.4%. In the polymer hybrid material, based on the total mass of the poly 1,2-dithiolane-3-octanoic acid segment and the polyether segment, the mass content of the polyether segment is 9.24%; the mass content of the coordinated iron ion is 0.57% of the poly 1,2-dithiolane-3-octanoic acid segment.

[0060] The polymer network hybrid material has an antibacterial rate of 2.53 against E. coli and 2.57 against S. aureus, and is an excellent intrinsic antibacterial material. Scratches on the surface of the polymer network hybrid material film can be quickly repaired within 30 minutes at 45°C.

[0061] Example 3

[0062] The polymerization method and post-treatment method are the same as in Example 1, except that: TA-PTHF 1k -TA (same as in Example 1) was added in an amount of 2.0 g, TA and TA-PTHF 1kThe molar ratio of -TA is 34.3. The yield of the polymer hybrid material is 99.8%. In the polymer hybrid material, based on the total mass of the poly 1,2-dithiolane-3-octanoic acid segment and the polyether segment, the mass content of the polyether segment is 11.80%; the mass content of the coordinated iron ion is 0.57% of the poly 1,2-dithiolane-3-octanoic acid segment.

[0063] The polymer network hybrid material has an antibacterial rate of 2.33 against E. coli and an antibacterial rate of 2.21 against S. aureus, and is an excellent intrinsic antibacterial material; scratches on the surface of the polymer network hybrid material film can be quickly repaired within 30 minutes at 45°C.

[0064] Example 4

[0065] TA-PTHF 2k -TA macromolecular monomer synthesis method is the same as Example 1, the difference is: TA amount is 2.06g, DMAP amount is 1.22g, EDCl amount is 2.01g, PTHF molecular weight is 2000g / mol. 2k The molar ratio of was 2.0, the molar ratio of DMAP to TA was 1.00, and the molar ratio of EDCl to TA was 1.05.

[0066] The polymerization method and post-treatment method are the same as in Example 1, except that: TA-PTHF 2k -TA added in an amount of 1.7 g, TA and TA-PTHF 2k The molar ratio of -TA is 68.9. The yield of the polymer hybrid material is 99.5%. In the polymer hybrid material, based on the total mass of the poly 1,2-dithiolane-3-octanoic acid segment and the polyether segment, the mass content of the polyether segment is 12.05%; the mass content of the coordinated iron ion is 0.58% of the poly 1,2-dithiolane-3-octanoic acid segment.

[0067] The polymer network hybrid material has an antibacterial rate of 1.87 against E. coli and 2.34 against S. aureus, and is an excellent intrinsic antibacterial material. Scratches on the surface of the polymer network hybrid material film can be quickly repaired within 30 minutes at 45°C.

[0068] Example 5

[0069] The polymerization method and post-treatment method are the same as in Example 4, except that: TA-PTHF 2k -TA (same as in Example 4) was added in an amount of 2.5 g, TA and TA-PTHF 1kThe molar ratio of -TA is 46.8. The yield of the polymer hybrid material is 99.7%. In the polymer hybrid material, based on the total mass of the poly 1,2-dithiolane-3-octanoic acid segment and the polyether segment, the mass content of the polyether segment is 16.58%; the mass content of the coordinated iron ion is 0.57% of the poly 1,2-dithiolane-3-octanoic acid segment.

[0070] The polymer network hybrid material has an antibacterial rate of 2.51 against E. coli and an antibacterial rate of 1.90 against S. aureus, and is an excellent intrinsic antibacterial material; scratches on the surface of the polymer network hybrid material film can be quickly repaired within 30 minutes at 45°C.

[0071] Example 6

[0072] The polymerization method and post-treatment method are the same as in Example 4, except that: TA-PTHF 2k -TA (same as in Example 4) was added in an amount of 3.4 g, TA and TA-PTHF 1k The molar ratio of -TA is 34.4. The yield of the polymer hybrid material is 98.5%. In the polymer hybrid material, based on the total mass of the poly 1,2-dithiolane-3-octanoic acid segment and the polyether segment, the mass content of the polyether segment is 21.04%; the mass content of the coordinated iron ion is 0.57% of the poly 1,2-dithiolane-3-octanoic acid segment.

[0073] The polymer network hybrid material has an antibacterial rate of 2.28 against E. coli and an antibacterial rate of 2.91 against S. aureus, and is an excellent intrinsic self-healing antibacterial material; scratches on the surface of the polymer network hybrid material film can be quickly repaired within 30 minutes at 45°C.

[0074] Example 7

[0075] The polymerization method and post-treatment method are the same as in Example 1, except that: TA-PTHF 1k -TA (same as in Example 1) was added in an amount of 2.0 g, the molar ratio of isopropanol to TA in the reaction system was 0.063, the molar ratio of FeCl3 to monomer was 0.044, and the molar ratio of TA to TA-PTHF was 0.063. 1k The molar ratio of -TA is 34.3. The yield of the polymer hybrid material is 99.5%. In the polymer hybrid material, based on the total mass of the poly 1,2-dithiolane-3-octanoic acid segment and the polyether segment, the mass content of the polyether segment is 11.80%; the mass content of the coordinated iron ion is 1.13% of the poly 1,2-dithiolane-3-octanoic acid segment.

[0076] The polymer network hybrid material has an antibacterial rate of 1.43 against E. coli and 1.38 against S. aureus, and is an excellent intrinsic self-healing antibacterial material. Scratches on the surface of the polymer network hybrid material film can be quickly repaired within 30 minutes at 45°C.

[0077] Example 8

[0078] The polymerization method and post-treatment method are the same as in Example 1, except that: TA-PTHF 1k -TA (same as in Example 1) was added in an amount of 2.0 g, the molar ratio of isopropanol to TA in the reaction system was 0.094, the molar ratio of FeCl3 to the monomer was 0.066, and the molar ratio of TA to TA-PTHF was 0.094. 1k The molar ratio of -TA is 34.3. The yield of the polymer hybrid material is 99.0%. In the polymer hybrid material, based on the total mass of the poly 1,2-dithiolane-3-octanoic acid segment and the polyether segment, the mass content of the polyether segment is 11.80%; the mass content of the coordinated iron ion is 1.70% of the poly 1,2-dithiolane-3-octanoic acid segment.

[0079] The polymer network hybrid material has an antibacterial rate of 1.42 against E. coli and 1.71 against S. aureus, and is an excellent intrinsic antibacterial material. Scratches on the surface of the polymer network hybrid material film can be quickly repaired within 30 minutes at 45°C.

[0080] Example 9

[0081] The polymerization method and post-treatment method are the same as in Example 4, except that: TA-PTHF 2k -TA (same as in Example 4) was added in an amount of 2.0 g, TA and TA-PTHF 1k The molar ratio of -TA is 58.5, and the polymerization reaction temperature is -10°C. The yield of the polymer hybrid material is 99.5%. In the polymer hybrid material, based on the total mass of the poly-1,2-dithiolane-3-octanoic acid segment and the polyether segment, the mass content of the polyether segment is 13.82%; the mass content of the coordinated iron ion is 0.58% of the poly-1,2-dithiolane-3-octanoic acid segment.

[0082] The polymer network hybrid material has an antibacterial rate of 2.31 against E. coli and 2.68 against S. aureus, and is an excellent intrinsic antibacterial material. Scratches on the surface of the polymer film can be quickly repaired within 30 minutes at 45°C.

[0083] Example 10

[0084] The polymerization method and post-treatment method are the same as in Example 1, except that: TA-PTHF1k -TA (same as in Example 1) was added in an amount of 2.0 g, TA and TA-PTHF 1k The molar ratio of -TA is 34.3, and the polymerization reaction temperature is 20°C. The yield of the polymer hybrid material is 98.5%. In the polymer hybrid material, based on the total mass of the poly-1,2-dithiolane-3-octanoic acid segment and the polyether segment, the mass content of the polyether segment is 11.80%; the mass content of the coordinated iron ion is 0.57% of the poly-1,2-dithiolane-3-octanoic acid segment.

[0085] The polymer network hybrid material has an antibacterial rate of 1.89 against E. coli and an antibacterial rate of 2.00 against S. aureus, and is an excellent intrinsic antibacterial self-healing material. Scratches on the surface of the polymer network hybrid material film can be quickly repaired within 30 minutes at 45°C.

[0086] Embodiment 11

[0087] The polymerization method and post-treatment method are the same as those in Example 1, except that the amount of TA added is 5.0 g, the molar ratio of tert-butyl chloride to TA in the reaction system is 0.053, the molar ratio of isopropanol to TA is 0.056, the molar ratio of FeCl3 to monomer is 0.040, and the molar ratio of TA to TA-PTHF is 0.054. 1k The molar ratio of -TA is 34.3. The yield of the polymer hybrid material is 98.5%. In the polymer hybrid material, based on the total mass of the poly 1,2-dithiolane-3-octanoic acid segment and the polyether segment, the mass content of the polyether segment is 11.80%; the mass content of the coordinated iron ion is 1.01% of the poly 1,2-dithiolane-3-octanoic acid segment.

[0088] The polymer network hybrid material has an antibacterial rate of 1.16 against E. coli and 1.25 against S. aureus, and is an intrinsic antibacterial material. Scratches on the surface of the polymer network hybrid material can be quickly repaired.

[0089] Example 12

[0090] The polymerization method and post-treatment method are the same as those in Example 1, except that 1.3 mL of TiCl4 / CH2Cl2 solution is added to initiate the polymerization. The molar ratio of tert-butyl chloride to TA in the reaction system is 0.027, the molar ratio of TiCl4 to TA is 0.027, and the molar ratio of TA to TA-PTHF is 0.027. 1k The molar ratio of -TA is 68.5. In the prepared polymer hybrid material, based on the total mass of the poly 1,2-dithiolane-3-octanoic acid segment and the polyether segment, the mass content of the polyether segment is 6.44%; the mass content of the coordinated titanium ion is 0.60% of the poly 1,2-dithiolane-3-octanoic acid segment.

[0091] The polymer network hybrid material has an antibacterial rate of 1.05 against E. coli and 1.02 against S. aureus, and is an intrinsic antibacterial material. Scratches on the surface of the polymer network hybrid material can be quickly repaired.

[0092] Example 13

[0093] The polymerization method and post-treatment method are the same as those in Example 12, except that 1.3 mL of SnCl4 / CH2Cl2 solution is added to initiate the polymerization. The molar ratio of tert-butyl chloride to TA in the reaction system is 0.027, the molar ratio of SnCl4 to TA is 0.027, and the molar ratio of TA to TA-PTHF is 0.027. 1k The molar ratio of -TA is 68.5. In the prepared polymer hybrid material, based on the total mass of the poly 1,2-dithiolane-3-octanoic acid segment and the polyether segment, the mass content of the polyether segment is 6.44%; the mass content of the coordinated tin ion is 1.50% of the poly 1,2-dithiolane-3-octanoic acid segment.

[0094] The polymer network hybrid material has an antibacterial rate of 1.05 against E. coli and 1.02 against S. aureus, and is an intrinsic antibacterial material. Scratches on the surface of the polymer network hybrid material can be quickly repaired.

[0095] The embodiments of the present invention have been described above, and the above description is exemplary, not exhaustive, and is not limited to the disclosed embodiments. Many modifications and changes will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments.

Claims

1. A polymer network hybrid material containing disulfide bonds and ether bonds, It is characterized in that The polymer network hybrid material is composed of a polydisulfide compound segment, a polyether segment and a coordinated metal ion; The polydisulfide chain segments and the polyether chain segments are connected via carboxylate covalent bonds to form a covalent cross-linked network, and some side carboxyl groups of the polydisulfide chain segments and the coordinated metal ions form a dynamic coordination cross-linked network via coordination bonds.

2. The polymer network hybrid material containing disulfide bonds and ether bonds according to claim 1, in, Based on the total mass of the polydisulfide compound segment and the polyether segment, the mass content of the polyether segment is 4 to 30%, preferably 5 to 25%, and more preferably 6 to 22%; The mass content of the coordinated metal ions is 0.3-2.0% of the polydisulfide compound chain segment, preferably 0.4-1.8%, and more preferably 0.5-1.6%.

3. The polymer network hybrid material containing disulfide bonds and ether bonds according to claim 1, in, The polydisulfide compound is a compound containing structural units derived from a 1,2-disulfide five-membered ring compound, and each structural unit is connected by a chemical bond; The 1,2-dithio five-membered ring compound is selected from at least one of 1,2-dithiolane-3-butyric acid, 1,2-dithiolane-3-hexanoic acid, 1,2-dithiolane-3-octanoic acid, 1,2-dithiolane-3-nonanoic acid, 1,2-dithiolane-4-carboxylic acid, 1,2-dithiolane-4-hydroxy-3-octanoic acid, 1,2-dithiolane-4-hydroxy-3-pentanoic acid, 1,2-dithiolane-4-hydroxy-3-butyric acid and 1,2-dithiolane-4-carbonyl-3-hexanoic acid; The polyether segment is at least one of a polyethylene oxide segment, a polyethylene glycol segment, a polypropylene oxide segment and a polytetrahydrofuran segment.

4. The polymer network hybrid material containing disulfide bonds and ether bonds according to claim 1, in, The coordinating metal ion is selected from Ti 4+ Sn 4+ , Fe 3+ and Al 3+ At least one of .

5. A method for preparing a polymer network hybrid material containing disulfide bonds and ether bonds according to any one of claims 1 to 4, It is characterized in that The steps include: (1) Synthesis of ester-functionalized polyethers containing 1,2-disulfide five-membered ring structural units at both ends Under nitrogen protection and stirring conditions, a double-terminal hydroxyl functionalized polyether is subjected to an esterification reaction with a 1,2-disulfide five-membered ring compound in a first organic solvent system containing a proton transfer agent and a dehydrating agent to obtain a double-terminal ester functionalized polyether containing a 1,2-disulfide five-membered ring structural unit; (2) Synthesis of polymer networks containing disulfide bonds and ether bonds Under nitrogen protection, the double-terminal ester-functionalized polyether containing 1,2-disulfide five-membered ring structural units synthesized in step (1) is used as a macromonomer, and a 1,2-disulfide five-membered ring compound is copolymerized in a second organic solvent system containing an initiator system to form a cross-linked network in which polydisulfide compound segments and polyether segments are connected by carboxylate covalent bonds; the initiator system is composed of an initiator, a metal-based co-initiator, and an optional oxygen-containing organic compound; (3) Synthesis of polymer network hybrid materials containing disulfide bonds and ether bonds After the copolymerization reaction is completed, a terminator is added to terminate the polymerization reaction, and the metal ions in the chain end counterions derived from the metal-based co-initiator are released and coordinated with part of the side carboxyl groups of the polydisulfide compound segments in the above-mentioned polymer network containing disulfide bonds and ether bonds, thereby in situ preparing the polymer network hybrid material containing disulfide bonds and ether bonds.

6. The preparation method according to claim 5, in, In step (1), the dehydrating agent is a carbodiimide compound, preferably at least one selected from N,N'-dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide, 1-ethyl-(3-dimethylaminopropyl)carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide and their hydrochloride, more preferably N,N'-dicyclohexylcarbodiimide and / or N,N'-diisopropylcarbodiimide hydrochloride; The proton transfer agent is a compound containing pyridine and / or a tertiary amine structure, preferably at least one selected from trimethylamine, triethylamine, triphenylamine, pyridine, 4-aminopyridine, 4-(N,N-dimethyl)pyridine and 4-(N,N-diethyl)pyridine, more preferably at least one selected from triethylamine, triphenylamine and 4-(N,N-dimethyl)pyridine; The first organic solvent is selected from at least one of dichloromethane, chloroform, dichloroethane, tetrahydrofuran, N,N-dimethylformamide and dimethyl sulfoxide.

7. The preparation method according to claim 5, in, In step (1), the molar ratio of the double-terminal hydroxyl functionalized polyether to the 1,2-disulfide five-membered ring compound is 1:2 to 1:2.5; The molar ratio of the proton transfer agent to the 1,2-disulfide five-membered ring compound is 1.0 to 1.1; The molar ratio of the dehydrating agent to the 1,2-disulfide five-membered ring compound is 1.0 to 1.1; The conditions of the esterification reaction include: reaction temperature of -30 to 30°C, preferably -20 to 25°C, and time of 2 to 24 hours, preferably 12 to 24 hours.

8. The preparation method according to claim 5, in, In step (2), the initiator is a monofunctional initiator or a bifunctional initiator, preferably at least one selected from tert-butyl chloride, cumyl chloride, p-dicumyl chloride, benzyl chloride, benzyl bromide, allyl chloride and allyl bromide; The metal-based co-initiator is a Lewis acid, preferably at least one selected from ferric chloride, titanium tetrachloride, tin tetrachloride, aluminum chloride, ethylaluminum dichloride, isobutylaluminum dichloride, ethylaluminum sesquichloride and isobutylaluminum sesquichloride; The oxygen-containing organic compound is selected from at least one of methanol, ethanol, n-propanol, isopropanol, isobutanol, tert-butanol, isopentanol, hexanol, 2-ethylhexanol, ethyl ether, propyl ether, isopropyl ether, methyl tert-butyl ether, n-butyl ether and isobutyl ether; The second organic solvent is a hydrocarbon and / or a halogenated hydrocarbon, preferably selected from at least one of pentane, cyclopentane, methylcyclopentane, hexane, methylcyclohexane, heptane, octane, methyl chloride, dichloromethane, ethylene dichloride, chloroform, ethyl chloride, dichloroethane, trichloroethane and carbon tetrachloride, more preferably selected from at least one of pentane, hexane, cyclohexane, methylcyclopentane, methylcyclohexane, heptane, octane, ethyl chloride, dichloromethane and dichloroethane.

9. The preparation method according to claim 5, in, In step (2), the molar ratio of the 1,2-disulfide five-membered ring compound to the double-terminal 1,2-disulfide five-membered ring ester functionalized polyether is 25 to 90, preferably 30 to 75; The molar ratio of the initiator to the 1,2-disulfide five-membered ring compound in the reaction system is 0.020 to 0.075, preferably 0.025 to 0.060; the molar ratio of the metal-based co-initiator to the 1,2-disulfide five-membered ring compound is 0.015 to 0.085, preferably 0.020 to 0.075; The conditions of the copolymerization reaction include: reaction temperature of -35 to 50°C, preferably -25 to 40°C, more preferably -15 to 30°C, reaction time of 1 to 60 min, preferably 1 to 20 min.

10. Use of the polymer network hybrid material containing disulfide bonds and ether bonds as described in any one of claims 1 to 4 or the polymer network hybrid material containing disulfide bonds and ether bonds obtained by the preparation method as described in any one of claims 5 to 9 in the field of biological protective films.

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