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CN110283320B - A kind of synthetic method of antibacterial hydrogel that can be hydrolyzed under weak alkaline - Google Patents

A kind of synthetic method of antibacterial hydrogel that can be hydrolyzed under weak alkaline Download PDF

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CN110283320B
CN110283320B CN201910393657.1A CN201910393657A CN110283320B CN 110283320 B CN110283320 B CN 110283320B CN 201910393657 A CN201910393657 A CN 201910393657A CN 110283320 B CN110283320 B CN 110283320B
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iodoacetate
chloroacetate
bromoacetate
glycol
tertiary amine
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CN110283320A (en
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韩金
陈钦越
沈宇鹏
马佳奇
冯祎平
钟明强
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Zhejiang University of Technology ZJUT
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    • C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
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Abstract

本发明公开了一种可在弱碱性下水解的抗菌水凝胶的合成方法，该方法为：在反应器中依次加入八乙烯基POSS、叔胺硫醇和干燥的四氢呋喃，然后将反应器用铝箔包起来，加入光引发剂后密封，用高纯度N2吹扫混合物以除去氧气，除去铝箔在365nm的紫外线照射下，室温搅拌反应1～12h。反应结束后，旋转蒸发除去溶剂和多余的叔胺硫醇，得到粘稠液体。取上述产物与双卤素的卤代烃酯和单卤素的卤代烃酯在室温下混合均匀后，反应一段时间，放置在膜具中既得到所述的固化凝胶，浸泡在超纯水里充分溶胀，得到产物。本发明得到的水凝胶成胶时间短、制备过程简单、可以在弱碱性下水解、有优异的抗菌效果，可以应用在生物敷料等领域。

Figure 201910393657

The invention discloses a method for synthesizing an antibacterial hydrogel that can be hydrolyzed under weak alkalinity. The method comprises the following steps: adding octavinyl POSS, tertiary amine mercaptan and dry tetrahydrofuran in sequence to a reactor, and then lining the reactor with aluminum foil Wrap it up, add photoinitiator and seal, purge the mixture with high-purity N2 to remove oxygen, remove aluminum foil, and react with stirring at room temperature for 1–12 h under UV irradiation at 365 nm. After the reaction, the solvent and excess tertiary amine thiol were removed by rotary evaporation to obtain a viscous liquid. After mixing the above product with the halogenated hydrocarbon ester of the dihalogen and the halogenated hydrocarbon ester of the monohalogen at room temperature, react for a period of time, place it in the membrane to obtain the cured gel, and soak it in ultrapure water. Fully swollen to obtain the product. The hydrogel obtained by the invention has short gel-forming time, simple preparation process, can be hydrolyzed in weak alkaline condition, has excellent antibacterial effect, and can be applied in the fields of biological dressings and the like.

Figure 201910393657

Description

Synthesis method of antibacterial hydrogel capable of being hydrolyzed under weak alkaline
Technical Field
The invention relates to a method for synthesizing antibacterial hydrogel which can be hydrolyzed under alkalescence, in particular to a gel polymer which contains quaternary ammonium salt, long-chain alkyl antibacterial groups, and silicon-oxygen-silicon bonds and ester bonds which can be hydrolyzed under alkalescence.
Background
The antibacterial hydrogel is an important antibacterial material and has important application in medical dressings, medical instrument coatings and tissue engineering. At present, common antibacterial polymers include quaternary ammonium salt polymers, quaternary phosphonium salt polymers, halogen amine polymers, guanidine polymers and the like. The ideal antibacterial hydrogel material should have efficient antibacterial activity, good biocompatibility, good biodegradability, simple and mild preparation method and low cost. However, such hydrogels having various properties at the same time are recently reported. It remains a challenge to develop new antimicrobial hydrogels that meet all-round requirements.
The sterilization principle of the general quaternary ammonium salt antibacterial polymer is that cations in the quaternary ammonium salt have certain interaction with microbial cells. And then acts on the lipid bilayer structure of the microbial cell membrane, thereby killing the microorganisms. The introduction of quaternary ammonium salt is generally carried out by the quaternization reaction of tertiary amine and halogenated alkane or halogen and tertiary amine, and the tertiary amine and halogen atom interact to form an ion structure, but at present, many quaternary ammonium salt antibacterial hydrogels have the defects of complicated preparation method, poor biodegradability, use of a large amount of solvents and the like, and still need to be researched in a deep effort.
The quaternary ammonium salt polymer synthesized by the invention synthesizes the antibacterial hydrogel simultaneously containing the quaternary ammonium salt and the long-chain alkyl, and the hydrogel has better antibacterial effect due to the synergistic effect of the long-chain alkyl and the quaternary ammonium salt. The product is a compound which is modified by octavinyl POSS through tertiary amine mercaptan and contains a plurality of tertiary amino groups, and halogenated hydrocarbon ester containing one or a plurality of halogens is directly mixed and crosslinked to form hydrogel. In the process of crosslinking, any solvent is not used, direct mixing is carried out, and the crosslinking speed is very quick. The polymer synthesized by the method contains two antibacterial factors, namely long-chain alkyl and quaternary ammonium salt, has a good antibacterial effect, is short in gelling time, can be hydrolyzed under alkalescence (usually the pH is about 8), and can be applied to the fields of biological dressings and the like.
Disclosure of Invention
The invention aims to provide a method for synthesizing antibacterial hydrogel which can be hydrolyzed under weak alkaline.
In order to realize the purpose, the following technical scheme is provided:
a method for synthesizing antibacterial hydrogel which can be hydrolyzed under weak alkaline comprises the following steps:
(1) sequentially adding octavinyl POSS, tertiary amine mercaptan and dry tetrahydrofuran into a reactor, wherein the molar ratio of the octavinyl POSS to the tertiary amine mercaptan is 1 (8-12); then, the reactor was wrapped with aluminum foil, added with photoinitiator, sealed, and treated with high purity N2And purging the mixture in the reactor to remove oxygen, then removing aluminum foil, and stirring and reacting for 1-12 h at room temperature under 365nm ultraviolet irradiation. After the reaction is finished, the solvent and the redundant tertiary amine mercaptan are removed by rotary evaporation to obtain viscous liquid.
(2) And (3) uniformly mixing the product with the halohydrocarbon ester of the double halogen and the halohydrocarbon ester of the single halogen at room temperature, placing the mixture in a film to obtain a solidified gel after reaction, and soaking the solidified gel in ultrapure water to fully swell to obtain the antibacterial hydrogel which can be hydrolyzed under weak alkaline.
In the above technical solution, preferably, the tertiary amine thiol is selected from, but not limited to, dimethylamino ethanethiol, dimethylamino butanethiol, dimethylamino pentanethiol, diethylaminoethanethiol, diethylaminobutanethiol, diethylaminopentanethiol, diethylaminoethanethiol, diethylaminobutanethiol, and diethylaminopentanethiol.
Preferably, the photoinitiator is selected from the group consisting of, but not limited to, diphenylethanone, benzoin diethyl ether, benzoin derivatives, benzil ketal derivatives, α -hydroxyalkylphenone, α -aminoalkylphenones, acylphosphine oxides, esterified oxime ketone compounds, aryl peroxy ester compounds, dialkoxyacetophenones, phenylacetic acid esters, diphenylethanones.
Preferably, the halohydrocarbon ester of bis-halogen is selected from propylene glycol chloroacetate, butylene glycol chloroacetate, pentylene glycol chloroacetate, hexylene glycol chloroacetate, heptylene glycol chloroacetate, octylene glycol chloroacetate, nonylene glycol chloroacetate, hexylene glycol chloroacetate, propylene glycol bromoacetate, butylene glycol bromoacetate, pentylene glycol bromoacetate, hexylene glycol bromoacetate, heptylene glycol bromoacetate, octylene glycol bromoacetate, nonylene glycol bromoacetate, sebacic glycol bromoacetate, propylene glycol iodoacetate, butylene glycol iodoacetate, pentylene glycol iodoacetate, hexylene glycol iodoacetate, heptylene glycol iodoacetate, octylene glycol iodoacetate, nonylene glycol iodoacetate, and sebacic glycol iodoacetate, but is not limited thereto.
Preferably, the monohalogen halohydrocarbon ester, propanol chloroacetate, pentanol chloroacetate, hexanol chloroacetate, heptanol chloroacetate, octanol chloroacetate, nonanol chloroacetate, decanol chloroacetate, undecanol chloroacetate, dodecanol chloroacetate, tridecanol chloroacetate, tetradecanol chloroacetate, pentadecanol chloroacetate, hexadecanol chloroacetate, propanol bromoacetate, pentanol bromoacetate, hexanol bromoacetate, heptanol bromoacetate, octanol bromoacetate, nonanol bromoacetate, decanol bromoacetate, undecanol bromoacetate, dodecanol bromoacetate, tridecanol bromoacetate, tetradecanol bromoacetate, pentadecanol bromoacetate, hexadecanol bromoacetate, propanol iodoacetate, pentanol iodoacetate, hexanol iodoacetate, heptanol iodoacetate, octanol iodoacetate, nonanol iodoacetate, decanol iodoacetate, Undecyl alcohol iodoacetate, dodecyl alcohol iodoacetate, tridecyl alcohol iodoacetate, tetradecyl alcohol iodoacetate, pentadecyl alcohol iodoacetate, and hexadecyl alcohol iodoacetate, but not limited thereto.
The invention has the advantages that the synthesis of the antibacterial gel has the characteristics of high speed, high efficiency, simple process, high yield and the like. The hydrogel has a good sterilization effect, can be hydrolyzed under a weak alkaline condition, is a good degradable environment-friendly polymer, and has application prospects in the fields of biomedical dressings and the like.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of a compound of octatertiary amino POSS synthesized with octavinyl POSS and dimethylaminoethanethiol in accordance with the present invention;
FIG. 2 is a fluorescence microscope image of the antimicrobial hydrogel of the present invention: (1) a, b, c and d respectively correspond to the antibacterial fluorescence micrographs of gels formed by different monohalogen halogenated hydrocarbon esters; (2) a, B, C, D represents the number of viable and dead bacteria corresponding to the number of viable and dead bacteria;
FIG. 3 is a graph of the hydrolytic weight loss of hydrogels for different mole ratios of Hexanediol Chloroacetate (HCA) and hexadecanol chloroacetate (CCA); the four curves are that the ratio of HCA to CCA is 4:0, 3:2, 2:4 and 1:6 from top to bottom;
FIG. 4 is a photograph of the product of the reaction of an octavinyl POSS modified with a tertiary amine thiol in accordance with the present invention with a halogen-containing halohydrocarbon ester.
Detailed Description
The principle of the invention is to utilize tertiary amine mercaptan and polyvinyl monomer to generate 'alkene-click' mercaptan reaction to generate compound containing poly tertiary amine. And mixing the compound of the poly tertiary amine and halogenated hydrocarbon ester containing one or more halogens to perform quaternization reaction to generate gel containing quaternary ammonium salt and long-chain alkyl. The quaternary ammonium salt has good antibacterial effect under the action of long-chain alkyl, and the hydrogel is easy to hydrolyze under the weak alkaline condition, because the ester bond is easier to hydrolyze than the common ester bond due to the strong electric absorbability of the quaternary ammonium when the carbon atom of the quaternary ammonium group is on the alpha-carbon atom.
The present invention will be further described with reference to the drawings and examples, and the objects and effects of the present invention will become more apparent.
Example 1:
octavinyl POSS (0.63g, 1mmol) and 3- (dimethylamino) -1-propanethiol (DPT) (1.19g, 10mmol), dried THF (5mL) were added sequentially to a 25mL flask. The flask was wrapped with aluminum foil and then photoinitiator DMPA (41mg, 0.16mmol) was added thereto. After sealing, with high purity N2Purging the mixture to remove oxygenAnd (4) qi. Then, the aluminum foil was removed, and the reaction was triggered at room temperature under 365nm ultraviolet irradiation. As the reaction proceeds, the octavinyl POSS gradually dissolves in solution. After 1 hour, the UV was turned off. Excess 3- (dimethylamino) -1-propanethiol was removed by evaporation in vacuo at 30 ℃. The yield of the resulting viscous liquid was 87.45%.
Directly mixing the obtained 1mmol of compound containing eight tertiary amines, 1mmol of hexanediol chloroacetate and 6mmol of hexadecanol chloroacetate, reacting for a period of time, and injecting into a membrane to obtain the gel containing quaternary ammonium salt and long-chain alkyl.
The whole reaction process can be represented by the following formula:
Figure BDA0002057454420000041
example 2:
octavinyl POSS (0.63g, 1mmol) and 3- (dimethylamino) -1-propanethiol (DPT) (1.19g, 10mmol), dried THF (5mL) were added sequentially to a 25mL flask. The flask was wrapped with aluminum foil and then photoinitiator DMPA (41mg, 0.16mmol) was added thereto. After sealing, with high purity N2The mixture is purged to remove oxygen. Then, the aluminum foil was removed, and the reaction was triggered at room temperature under 365nm ultraviolet irradiation. As the reaction proceeds, the octavinyl POSS gradually dissolves in solution. After 1 hour, the UV was turned off. Excess 3- (dimethylamino) -1-propanethiol was removed by evaporation in vacuo at 30 ℃. The yield of the resulting viscous liquid was 87.45%.
Directly mixing the obtained 1mmol of compound containing eight tertiary amines, 1mmol of hexanediol chloroacetate and 6mmol of tetradecanol chloroacetate, reacting for a period of time, and injecting into a membrane to obtain the gel containing quaternary ammonium salt and long-chain alkyl.
Example 3:
octavinyl POSS (0.63g, 1mmol) and 3- (dimethylamino) -1-propanethiol (DPT) (1.19g, 10mmol), dried THF (5mL) were added sequentially to a 25mL flask. The flask was wrapped with aluminum foil and then photoinitiator DMPA (41mg, 0) was added thereto.16 mmol). After sealing, with high purity N2The mixture is purged to remove oxygen. Then, the aluminum foil was removed, and the reaction was triggered at room temperature under 365nm ultraviolet irradiation. As the reaction proceeds, the octavinyl POSS gradually dissolves in solution. After 1 hour, the UV was turned off. Excess 3- (dimethylamino) -1-propanethiol was removed by evaporation in vacuo at 30 ℃. The yield of the resulting viscous liquid was 87.45%.
Directly mixing the obtained 1mmol of compound containing eight tertiary amines, 1mmol of hexanediol chloroacetate and 6mmol of dodecanol chloroacetate, reacting for a period of time, and injecting into a membrane to obtain the gel containing quaternary ammonium salt and long-chain alkyl.
Example 4:
octavinyl POSS (0.63g, 1mmol) and 3- (dimethylamino) -1-propanethiol (DPT) (1.19g, 10mmol), dried THF (5mL) were added sequentially to a 25mL flask. The flask was wrapped with aluminum foil and then photoinitiator DMPA (41mg, 0.16mmol) was added thereto. After sealing, with high purity N2The mixture is purged to remove oxygen. Then, the aluminum foil was removed, and the reaction was triggered at room temperature under 365nm ultraviolet irradiation. As the reaction proceeds, the octavinyl POSS gradually dissolves in solution. After 1 hour, the UV was turned off. Excess 3- (dimethylamino) -1-propanethiol was removed by evaporation in vacuo at 30 ℃. The yield of the resulting viscous liquid was 87.45%.
Directly mixing the obtained 1mmol of compound containing eight tertiary amines, 1mmol of hexanediol chloroacetate and 6mmol of decaethanol chloroacetate, reacting for a period of time, and injecting into a membrane to obtain the gel containing quaternary ammonium salt and long-chain alkyl.
Example 5:
octavinyl POSS (0.63g, 1mmol) and 3- (dimethylamino) -1-propanethiol (DPT) (1.19g, 10mmol), dried THF (5mL) were added sequentially to a 25mL flask. The flask was wrapped with aluminum foil and then photoinitiator DMPA (41mg, 0.16mmol) was added thereto. After sealing, with high purity N2The mixture is purged to remove oxygen. Then, the aluminum foil was removed, and the reaction was triggered at room temperature under 365nm ultraviolet irradiation. As the reaction proceeds, octa-ethylThe alkenyl POSS gradually dissolved in solution. After 1 hour, the UV was turned off. Excess 3- (dimethylamino) -1-propanethiol was removed by evaporation in vacuo at 30 ℃. The yield of the resulting viscous liquid was 87.45%.
Directly mixing the obtained 1mmol of compound containing eight tertiary amines, 2mmol of hexanediol chloroacetate and 4mmol of hexadecanol chloroacetate, reacting for a period of time, and injecting into a membrane to obtain the gel containing quaternary ammonium salt and long-chain alkyl.
Example 6:
octavinyl POSS (0.63g, 1mmol) and 3- (dimethylamino) -1-propanethiol (DPT) (1.19g, 10mmol), dried THF (5mL) were added sequentially to a 25mL flask. The flask was wrapped with aluminum foil and then photoinitiator DMPA (41mg, 0.16mmol) was added thereto. After sealing, with high purity N2The mixture is purged to remove oxygen. Then, the aluminum foil was removed, and the reaction was triggered at room temperature under 365nm ultraviolet irradiation. As the reaction proceeds, the octavinyl POSS gradually dissolves in solution. After 1 hour, the UV was turned off. Excess 3- (dimethylamino) -1-propanethiol was removed by evaporation in vacuo at 30 ℃. The yield of the resulting viscous liquid was 87.45%.
Directly mixing the obtained 1mmol of compound containing eight tertiary amines, 3mmol of hexanediol chloroacetate and 2mmol of hexadecanol chloroacetate, reacting for a period of time, and injecting into a membrane to obtain the gel containing quaternary ammonium salt and long-chain alkyl.
Example 7:
octavinyl POSS (0.63g, 1mmol) and 3- (dimethylamino) -1-propanethiol (DPT) (1.19g, 10mmol), dried THF (5mL) were added sequentially to a 25mL flask. The flask was wrapped with aluminum foil and then photoinitiator DMPA (41mg, 0.16mmol) was added thereto. After sealing, with high purity N2The mixture is purged to remove oxygen. Then, the aluminum foil was removed, and the reaction was triggered at room temperature under 365nm ultraviolet irradiation. As the reaction proceeds, the octavinyl POSS gradually dissolves in solution. After 1 hour, the UV was turned off. Excess 3- (dimethylamino) -1-propanethiol was removed by evaporation in vacuo at 30 ℃. The yield of the resulting viscous liquid was 87.45%.
Directly mixing the obtained 1mmol of compound containing eight tertiary amines and 4mmol of hexanediol chloroacetate, reacting for a period of time, and injecting into a membrane to obtain the gel containing quaternary ammonium salt and long-chain alkyl.
Example 8:
octavinyl POSS (0.63g, 1mmol) and 3- (dimethylamino) -1-propanethiol (DPT) (1.19g, 10mmol), dried THF (5mL) were added sequentially to a 25mL flask. The flask was wrapped with aluminum foil and then photoinitiator DMPA (41mg, 0.16mmol) was added thereto. After sealing, with high purity N2The mixture is purged to remove oxygen. Then, the aluminum foil was removed, and the reaction was triggered at room temperature under 365nm ultraviolet irradiation. As the reaction proceeds, the octavinyl POSS gradually dissolves in solution. After 1 hour, the UV was turned off. Excess 3- (dimethylamino) -1-propanethiol was removed by evaporation in vacuo at 30 ℃. The yield of the resulting viscous liquid was 87.45%.
Directly mixing the obtained 1mmol of compound containing eight tertiary amines, 2mmol of butanediol chloroacetate and 4mmol of dodecanol chloroacetate, reacting for a period of time, and injecting into a membrane to obtain the gel containing quaternary ammonium salt and long-chain alkyl.
Example 9:
octavinyl POSS (0.63g, 1mmol) and 2- (dimethylamino) -1-ethanethiol (1.05g, 10mmol), dry THF (5mL) were added sequentially to a 25mL flask. The flask was wrapped with aluminum foil and then photoinitiator DMPA (41mg, 0.16mmol) was added thereto. After sealing, with high purity N2The mixture is purged to remove oxygen. Then, the aluminum foil was removed, and the reaction was triggered at room temperature under 365nm ultraviolet irradiation. As the reaction proceeds, the octavinyl POSS gradually dissolves in solution. After 1 hour, the UV was turned off. Excess 2- (dimethylamino) -1-ethanethiol was removed by evaporation in vacuo at 30 ℃. The yield of the obtained viscous liquid was 91.09%.
Directly mixing the obtained 1mmol of compound containing eight tertiary amines, 1mmol of hexanediol bromoacetate and 6mmol of hexadecanol bromoacetate, reacting for a period of time, and injecting into a membrane to obtain the gel containing quaternary ammonium salt and long chain alkyl.
Example 10:
octavinyl POSS (0.63g, 1mmol) and 3- (dimethylamino) -1-propanethiol (DPT) (1.19g, 10mmol), dried THF (5mL) were added sequentially to a 25mL flask. The flask was wrapped with aluminum foil, and then a uv light initiator dialkoxyacetophenone (34mg, 0.16mmol) was added thereto. After sealing, with high purity N2The mixture is purged to remove oxygen. Then, the aluminum foil was removed, and the reaction was triggered at room temperature under 365nm ultraviolet irradiation. As the reaction proceeds, the octavinyl POSS gradually dissolves in solution. After 2 hours, the UV was turned off. Excess 3- (dimethylamino) -1-propanethiol was removed by evaporation in vacuo at 30 ℃ to give a viscous liquid in 81.23% yield.
Directly mixing the obtained 1mmol of compound containing eight tertiary amines, 2mmol of hexanediol bromoacetate and 4mmol of hexadecanol bromoacetate, reacting for a period of time, and injecting into a membrane to obtain the gel containing quaternary ammonium salt and long chain alkyl.
Example 11:
octavinyl POSS (0.63g, 1mmol) and 4- (dimethylamino) -1-butanethiol (DPT) (1.43g, 12mmol), dried THF (5mL) were added sequentially to a 25mL flask. The flask was wrapped with aluminum foil, and then photoinitiator 1173 (2-hydroxy-2-methyl-1-phenyl-1-propanone 26.3mg, 0.16mmol) was added thereto. After sealing, with high purity N2The mixture is purged to remove oxygen. Then, the aluminum foil was removed, and the reaction was triggered at room temperature under 365nm ultraviolet irradiation. As the reaction proceeds, the octavinyl POSS gradually dissolves in solution. After 4 hours, the UV was turned off. Excess 3- (dimethylamino) -1-propanethiol was removed by evaporation in vacuo at 30 ℃. The yield of the obtained viscous liquid was 85.15%.
Directly mixing the obtained 1mmol of compound containing eight tertiary amines, 1mmol of butanediol bromoacetate and 6mmol of tetradecanol bromoacetate, reacting for a period of time, and injecting into a membrane to obtain gel containing quaternary ammonium salt and long-chain alkyl.
Example 12:
octavinyl POSS (0.63g,1mmol) and 2- (dimethylamino) -1-ethanethiol (1.05g, 10mmol), dry THF (5mL) were added sequentially to a 25mL flask. The flask was wrapped with aluminum foil and then photoinitiator 1173 was added thereto. After sealing, with high purity N2The mixture is purged to remove oxygen. Then, the aluminum foil was removed, and the reaction was triggered at room temperature under 365nm ultraviolet irradiation. As the reaction proceeds, the octavinyl POSS gradually dissolves in solution. After 1 hour, the UV was turned off. Excess 2- (dimethylamino) -1-ethanethiol was removed by evaporation in vacuo at 30 ℃. The yield of the obtained viscous liquid was 91.09%.
Directly mixing the obtained 1mmol of compound containing eight tertiary amines, 3mmol of propylene glycol chloroacetate and 2mmol of cetyl chloroacetate, reacting for a period of time, and injecting into a membrane to obtain the gel containing quaternary ammonium salt and long-chain alkyl.
The killing effect of the hydrogel prepared by the method on staphylococcus aureus is shown in figure 2, wherein a, b, c and d respectively correspond to example 4, example 3, example 2 and example 1, and the antibacterial ability is continuously improved along with the increase of the length of the carbon chain of the halogenated hydrocarbon ester of the monohalogen, wherein when the length of the carbon chain is more than or equal to 12, the hydrogel shows good antibacterial effect; the hydrolysis of the hydrogel in PBS buffer at pH 8 is shown in fig. 3, where the four curves are, from top to bottom, Hexanediol Chloroacetate (HCA) and hexadecanol chloroacetate (CCA) in molar ratios of 4:0, 3:2, 2:4, 1:6, corresponding to example 7, example 6, example 5, example 1, respectively. It can be seen that the greater the weight loss ratio of the hydrogel as the content of the halohydrocarbon ester of dihalogen is reduced, that is, the less the content of halohydrocarbon ester of dihalogen, the more easily the hydrogel is hydrolyzed.

Claims (4)

1. A method for synthesizing antibacterial hydrogel which can be hydrolyzed under weak alkaline is characterized by comprising the following steps:
(1) sequentially adding octavinyl POSS, tertiary amine mercaptan and dry tetrahydrofuran into a reactor, wherein the molar ratio of the octavinyl POSS to the tertiary amine mercaptan is 1 (8-12); then the reactor was wrapped with aluminum foilAdding photoinitiator, sealing, and using high-purity N2Purging the mixture in the reactor to remove oxygen, removing aluminum foil, stirring at room temperature for reaction for 1-12 h under the irradiation of ultraviolet rays below 365nm, and after the reaction is finished, performing rotary evaporation to remove the solvent and redundant tertiary amine mercaptan to obtain viscous liquid;
(2) mixing the viscous liquid with halohydrocarbon ester of double halogen and halohydrocarbon ester of single halogen at room temperature, reacting, placing in a membrane to obtain solidified gel, soaking in ultrapure water for full swelling, and obtaining antibacterial hydrogel which can be hydrolyzed under weak alkaline;
the halohydrocarbon ester of the double halogen is selected from propylene glycol chloroacetate, butylene glycol chloroacetate, pentylene glycol chloroacetate, hexylene glycol chloroacetate, heptylene glycol chloroacetate, octylene glycol chloroacetate, nonylene glycol chloroacetate, decylene glycol chloroacetate, propylene glycol bromoacetate, butylene glycol bromoacetate, pentylene glycol bromoacetate, hexylene glycol bromoacetate, heptylene glycol bromoacetate, octylene glycol bromoacetate, nonylene glycol bromoacetate, decylene glycol bromoacetate, propylene glycol iodoacetate, butylene glycol iodoacetate, pentylene glycol iodoacetate, hexylene glycol iodoacetate, heptylene glycol iodoacetate, octylene glycol iodoacetate, nonylene glycol iodoacetate, decylene glycol iodoacetate;
the monohalogen halohydrocarbon ester is selected from propanol chloroacetate, pentanol chloroacetate, hexanol chloroacetate, heptanol chloroacetate, octanol chloroacetate, nonanol chloroacetate, decanol chloroacetate, undecanol chloroacetate, dodecanol chloroacetate, tridecanol chloroacetate, tetradecanol chloroacetate, pentadecanol chloroacetate, hexadecanol chloroacetate, propanol bromoacetate, pentanol bromoacetate, hexanol bromoacetate, heptanol bromoacetate, octanol bromoacetate, nonanol bromoacetate, decanol bromoacetate, undecanol bromoacetate, dodecanol bromoacetate, tridecanol bromoacetate, tetradecanol bromoacetate, pentadecanol bromoacetate, hexadecanol bromoacetate, propanol iodoacetate, pentanol iodoacetate, hexanol iodoacetate, heptanol iodoacetate, octanol iodoacetate, nonanol iodoacetate, decanol iodoacetate, undecanol iodoacetate, hexadecanol iodoacetate, pentanol iodoacetate, hexanol iodoacetate, heptanol iodoacetate, octanol iodoacetate, nonanol iodoacetate, decanol iodoacetate, undecanol iodoacetate, and mixtures thereof, Dodecyl alcohol iodoacetate, tridecyl alcohol iodoacetate, tetradecyl alcohol iodoacetate, pentadecyl alcohol iodoacetate, and hexadecyl alcohol iodoacetate.
2. The method for synthesizing the antibacterial hydrogel capable of being hydrolyzed under weak alkaline as claimed in claim 1, wherein the tertiary amine thiol is selected from the group consisting of dimethylaminoethanethiol, dimethylaminopropylthiol, dimethylaminobutanethiol, dimethylaminopentylthiol, diethylaminoethanethiol, diethylaminopropanethiol, diethylaminobutanethiol, diethylaminopentalthiol, dipropylaminopropylthiol, dipropylaminobutanthiol, and dipropylamipentalthiol.
3. The method for synthesizing an antibacterial hydrogel hydrolysable under weak alkaline as claimed in claim 1, wherein the photoinitiator is selected from the group consisting of diphenyl acetone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, benzoin dipropyl ether, benzoin derivatives, benzil ketal derivatives, α -hydroxyalkylphenone, α -aminoalkylphenone, acylphosphine oxide, esteroxime ketone compounds, aryl peroxy ester compounds, dialkoxypropiophenone, phenylpropionyl propionate.
4. An antibacterial hydrogel which is hydrolysable at weak alkaline, characterized in that it is obtained by the method according to any one of claims 1 to 3.
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