CN112239513A - Intrinsic self-repairing bactericidal polymer and preparation method thereof - Google Patents

Intrinsic self-repairing bactericidal polymer and preparation method thereof Download PDF

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CN112239513A
CN112239513A CN201910649345.2A CN201910649345A CN112239513A CN 112239513 A CN112239513 A CN 112239513A CN 201910649345 A CN201910649345 A CN 201910649345A CN 112239513 A CN112239513 A CN 112239513A
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repairing
self
parts
polymer
bactericidal
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CN112239513B (en
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傅佳骏
王成
沈涛
张雅娜
徐建华
陈骄阳
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Nanjing University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/44—Preparation of metal salts or ammonium salts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals

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Abstract

The invention discloses an intrinsic self-repairing bactericidal polymer and a preparation method thereof. The method takes hydroxyethyl acrylate, polyethylene glycol acrylate and 4-vinylpyridine as monomers, 1, 4-butanediol diacrylate as a covalent cross-linking agent unit, and performs quaternization on pyridine by 1-bromobutane after azo-diisobutyronitrile free radical copolymerization to prepare the intrinsic self-repairing type hydrophilic bactericidal polymer. The polymer of the invention has the room temperature fast self-repairing capability and simultaneously shows excellent sterilization performance, can realize fast repair without any external stimulus at room temperature, has the contact sterilization efficiency of over 99 percent, and has wide application prospect in the fields of medical implantation, biosensing, maritime work equipment and the like.

Description

Intrinsic self-repairing bactericidal polymer and preparation method thereof
Technical Field
The invention relates to an intrinsic self-repairing bactericidal polymer and a preparation method thereof, belonging to the technical field of flexible self-repairing materials and bactericidal materials.
Background
Biofouling refers to the action of bacteria and the like that adsorb on the surface of a material and affect the performance of the material, and has attracted much attention because of its harm to the aspects of biomedical, marine equipment, water purification systems, biosensors, and the like. For example, in the field of marine equipment, biofouling can accelerate equipment aging, resulting in significant economic losses; the purification efficiency is reduced in the aspect of a water purification system; in the field of biosensors, signal detection is disturbed.
Since most bacterial cell walls are negatively charged, 70% of them are phosphatidylethanolamines, most antimicrobial polymers are positively charged. The mechanism of action of cationic bactericides is the disruption of the bacterial cell wall or cytoplasmic membrane. The quaternary ammonium salt polymer is a cationic bactericide which is widely applied. However, in actual use, the sterilizing material is easily damaged by collision, abrasion, and the like, resulting in loss of the antifouling function.
Inspired by the healing process of natural living organisms, self-repairing materials can repair damage in an autonomous or non-autonomous manner, thereby restoring the original structure and function. Self-healing properties are generally achieved using supramolecular bonds (e.g., hydrogen bonds, ionic interactions, metal coordination bonds, host-guest interactions, etc.) and covalent bonds (e.g., Diels-Alder, trizolineiodisease brick, etc.). Compared to covalent cross-linking, supramolecular cross-linking has been extensively studied because of its ability to achieve endogenous and multiple lesion self-repair. Jianhua Xu et al prepared room temperature self-repairing anticorrosive material by using multiple hydrogen bonds inside polyurethane, can realize double recovery of mechanical properties and anticorrosive properties after damage (Xu J H, YE S, DING C D, et al. journal of Materials Chemistry a, 2018). Yibin Liu et al, prepared a biomimetic self-healing superhydrophobic film from PDMS and PFMA by free radical polymerization, restored the superhydrophobic properties of the surface after damage repair (LIU Y, GU H, JIA Y, et al. Chemical Engineering Journal,2019,356: 318-.
Disclosure of Invention
The invention aims to provide an intrinsic self-repairing bactericidal polymer capable of realizing self-repairing at room temperature and high stability and a preparation method thereof.
The technical scheme for realizing the purpose of the invention is as follows:
the preparation method of intrinsic self-repairing bactericidal polymer comprises using hydroxyethyl acrylate (HEA) and polyethylene glycol acrylate (PEGA)480) And 4-vinylpyridine (4-VP) is used as a monomer, 1, 4-butanediol diacrylate (BDDA) is used as a covalent cross-linking agent unit, the pyridine is quaternized by 1-bromobutane after the free radical copolymerization of Azobisisobutyronitrile (AIBN), and the method comprises the following specific steps:
according to parts by weight, 700-800 parts of HEA, 50 parts of PEGA480, 100-200 parts of 4-VP, 10 parts of AIBN and 35-55 parts of BDDA are dissolved in 10000-20000 parts of N, N-Dimethylformamide (DMF), the mixture is subjected to freeze thawing and deoxygenation, and then is subjected to reaction at 60-80 ℃ for 6-8 hours, after the reaction is finished, a polymerization inhibitor is added and is precipitated in glacial ethyl ether, 1-bromobutane is added, and the mixture is subjected to quaternization reaction with 4-vinylpyridine (4-VP) at 80-90 ℃ for more than 48 hours, after the reaction is finished, the residual 1-bromobutane is removed under reduced pressure, and the intrinsic self-repairing type bactericidal polymer film is obtained by drying and film forming.
The polymerization inhibitor is a polymerization inhibitor which is conventionally used in the field and can be tetrachlorobenzoquinone or 2, 6-di-tert-butyl-4-methylphenol.
Preferably, the molar weight of the 1-bromobutane is more than 3 times that of the 4-vinylpyridine.
Preferably, the drying temperature is 60-80 ℃.
The invention also provides the intrinsic self-repairing bactericidal polymer prepared by the preparation method.
Compared with the prior art, the invention has the following advantages:
(1) the polymer of the invention has a large number of supermolecular bonds, including mutual force between hydrogen bonds and ions, so that the polymer has the capability of quick self-repairing at room temperature, can be quickly repaired without any external stimulus, can repair scratches within 30 minutes, improve the service cycle and greatly reduce the use cost.
(2) The invention has the rapid self-repairing capability and simultaneously shows excellent sterilization performance, the contact sterilization efficiency is over 99 percent, and the invention can be applied to the fields of medical implantation, biosensing, maritime work equipment and the like.
Drawings
FIG. 1 is a schematic structural view of an intrinsic self-repairing bactericidal polymer of the present invention.
FIG. 2 shows the infrared spectra before and after quaternization of the intrinsically self-repairing bactericidal polymer prepared in example 1.
FIG. 3 is a DSC curve before and after quaternization of the intrinsically self-repairing bactericidal polymer prepared in example 1.
Fig. 4 is an image before and after scratch repair of the intrinsic self-repairing type bactericidal polymer film prepared in example 1.
Fig. 5 is an image before and after scratch repair of the intrinsic self-repairing type bactericidal polymer film prepared in comparative example 1.
FIG. 6 is a photograph showing the plate count of bacteria after the contact of the intrinsic self-repairing type sterilization polymer films prepared in example 1, example 2 and comparative example 1 with the bacteria.
Fig. 7 is a graph showing the antibacterial activity analysis of the intrinsic self-repairing type bactericidal polymer films obtained in example 1, example 2 and comparative example 1.
Detailed Description
The present invention will be described in more detail with reference to the following examples and the accompanying drawings.
Example 1
Mixing HEA (3.550g, 30.6mmol), PEGA480(0.96g, 2mmol), 4-VP (0.63g, 6mmol), BDDA (0.277g, 1.4mmol), AIBN (66mg, 0.4mmol) and 20mL DMF were mixed together and added to a 50mL Schlenk tube, stirred for 20 minutes to mix well and then freeze-thawed and degassed for 3 cycles, then heated in a 75 deg.C oil bath for 6h and then 0.2g MEHQ was added to stop the reaction. The copolymer was precipitated in glacial ethyl ether. Subsequently, p (HEA-co-PEGA)480-co-4VP) was dissolved in 20mL DMF and added to a 50mL round bottom flask with N2Purging for 30 minutes, adding dropwise an excess of 1-bromobutane to the solution andheated in an oil bath at 80 ℃ for 48 hours. And distilling the residual 1-bromobutane under reduced pressure, and directly drying the obtained copolymer solution in a polytetrafluoroethylene mold to form a film so as to obtain the intrinsic self-repairing bactericidal polymer film.
Example 2
Mixing HEA (3.318g, 28.6mmol), PEGA480(0.96g, 2mmol), 4-VP (0.84g, 8mmol), BDDA (0.277g, 1.4mmol), AIBN (66mg, 0.4mmol) and 20mL DMF were mixed together and added to a 50mL Schlenk tube, stirred for 20 minutes to mix well and then freeze-thawed and degassed for 3 cycles, then heated in a 75 deg.C oil bath for 6h and then 0.2g MEHQ was added to stop the reaction. The copolymer was precipitated in glacial ethyl ether. Subsequently, p (HEA-co-PEGA)480-co-4VP) was dissolved in 20mL DMF and added to a 50mL round bottom flask with N2Purge for 30 minutes, add excess 1-bromobutane dropwise to the solution and heat in an oil bath at 80 ℃ for 48 hours. And distilling the residual 1-bromobutane under reduced pressure, and directly drying the obtained copolymer solution in a polytetrafluoroethylene mold to form a film so as to obtain the intrinsic self-repairing bactericidal polymer film.
Comparative example 1
Mixing HEA (3.782g, 32.6mmol), PEGA480(0.96g, 2mmol), 4-VP (0.42g, 4mmol), BDDA (0.277g, 1.4mmol), AIBN (66mg, 0.4mmol) and 20mL DMF were mixed together and added to a 50mL Schlenk tube, stirred for 20 minutes to mix well and then freeze-thawed and degassed for 3 cycles, then heated in a 75 deg.C oil bath for 6h and then 0.2g MEHQ was added to stop the reaction. The copolymer was precipitated in glacial ethyl ether. Subsequently, p (HEA-co-PEGA)480-co-4VP) was dissolved in 20mL DMF and added to a 50mL round bottom flask with N2Purge for 30 minutes, add excess 1-bromobutane dropwise to the solution and heat in an oil bath at 80 ℃ for 48 hours. And distilling the residual 1-bromobutane under reduced pressure, and directly drying the obtained copolymer solution in a polytetrafluoroethylene mold to form a film so as to obtain the intrinsic self-repairing bactericidal polymer film.
Comparative example 2
Mixing HEA (3.550g, 30.6mmol), PEGA480(0.96g, 2mmol), 4-VP (0.63g, 6mmol), BDDA (0.396g, 2mmol), AIBN (66mg, 0.4mmol) and 20mL DMF were mixed together and added to a 50mL Schlenk tubeAfter stirring for 20 minutes to mix thoroughly, it was freeze-thawed and degassed for 3 cycles, then heated in an oil bath at 75 ℃ for 6 hours, and then 0.2g of MEHQ was added to terminate the reaction. The copolymer was precipitated in glacial ethyl ether. Subsequently, p (HEA-co-PEGA)480-co-4VP) was dissolved in 20mL DMF and added to a 50mL round bottom flask with N2Purge for 30 minutes, add excess 1-bromobutane dropwise to the solution and heat in an oil bath at 80 ℃ for 48 hours. And distilling the residual 1-bromobutane under reduced pressure, and directly drying the obtained copolymer solution in a polytetrafluoroethylene mold to form a film so as to obtain the intrinsic self-repairing bactericidal polymer film.
Characterization 1: structural and thermodynamic characterization
A Bruker Tensor II Fourier transform infrared spectrometer is adopted to test the structure of the sample, and the test range is as follows: 4000-400 cm-1. The thermal property of the polymer in the temperature range of-50 to 250 ℃ is researched by adopting differential scanning calorimetry (American DSC25TA instrument), and the heating rate is 10 ℃/min.
In FIG. 2, 1600cm of the inherently self-healing bactericidal polymer prepared in example 1 before quaternization-1The stretching vibration of C ═ N on the corresponding pyridine ring was completely shifted to 1640cm after quaternization-1It was demonstrated that the quaternization reaction proceeded sufficiently. FIG. 3 is a Differential Scanning Calorimetry (DSC) heating curve before and after quaternization of the intrinsically self-healing bactericidal polymer prepared in example 1. The glass transition temperature (Tg) of the polymer is increased from-24.5 ℃ before quaternization to-12.7 ℃, which shows that physical crosslinking is increased after quaternization to inhibit the fluidity of a chain segment, and the heating curve of the polymer after quaternization has a wider endothermic peak between 170 ℃ and 220 ℃, which is caused by the fact that the pyridine ion associate absorbs heat to melt and the size of the associate is not uniform.
And (2) characterization: self-repair and Sterilization Performance evaluation
Scratch test: a scratch having a width of about 10 μm was formed on the surface of the intrinsic self-repairing bactericidal polymer film obtained in example 1 using a scalpel, and the scratch disappeared after being maintained under ambient conditions (T25 ℃; RH 30%) for 15 minutes, as shown in fig. 4, with a scale of 100 μm. Fig. 5 (scale 100 μm) shows that scratches of the polymer film prepared in comparative example 2 were difficult to repair within 24 hours due to excessive crosslinking to inhibit the flow of the segments.
The intrinsic self-repairing bactericidal polymers prepared in the examples and comparative examples were subjected to bactericidal experiments: using Staphylococcus aureus (S) and Escherichia coli (E) as model bacteria, 1ml of the bacterial suspension was collected by centrifugation and washed 3 times with PBS. It was then resuspended in PBS and diluted to 10 deg.C8CFU/mL. Mu.l of the diluted bacterial suspension was added dropwise to the samples (20 mm. times.20 mm. times.1 mm), the samples were placed in a sterile six-well plate and covered with the same samples to ensure that the bacterial suspension covered the entire surface, after incubation for 1 hour at RH 90% and 37 ℃, each sample was washed with 2mL PBS to suspend live bacteria, diluted for agar plating, and then incubated for 18 hours at RH 80% and 37 ℃, and 3 repeats of averaging. SS 316L stainless steel was used as a control.
The antibacterial rate was calculated using the following formula: kill% ((CFU))Control-CFUPolymer)/CFUControl×100％
As is clear from the agar culture photograph in fig. 6 and the bactericidal activity chart in fig. 7, the contact bactericidal ratio of the intrinsic self-repairing bactericidal polymer obtained in example exceeds 95%, and the bactericidal performance of the intrinsic self-repairing bactericidal polymer obtained in example 1 and example 2 exceeds 99%.

Claims (5)

1. The preparation method of the intrinsic self-repairing bactericidal polymer is characterized by comprising the following specific steps:
according to parts by weight, 700-800 parts of HEA, 50 parts of PEGA480, 100-200 parts of 4-VP, 10 parts of AIBN and 35-55 parts of BDDA are dissolved in 10000-20000 parts of DMF, after freeze thawing and deoxygenation, the mixture reacts at 60-80 ℃ for 6-8 hours, after the reaction is finished, a polymerization inhibitor is added and is separated out in ethyl glacial ether, 1-bromobutane is added, quaternization reaction is carried out on the mixture and 4-vinylpyridine at 80-90 ℃, the reaction is carried out for more than 48 hours, after the reaction is finished, the residual 1-bromobutane is removed under reduced pressure, and the intrinsic self-repairing type bactericidal polymer film is obtained by drying and film forming.
2. The method according to claim 1, wherein the polymerization inhibitor is selected from tetrachlorobenzoquinone and 2, 6-di-tert-butyl-4-methylphenol.
3. The method according to claim 1, wherein the molar amount of 1-bromobutane is more than 3 times that of 4-vinylpyridine.
4. The preparation method according to claim 1, wherein the drying temperature is 60-80 ℃.
5. An intrinsically self-repairing bactericidal polymer prepared by the preparation method according to any one of claims 1 to 4.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090311302A1 (en) * 2005-08-24 2009-12-17 Youngblood Jeffrey P Hydrophilized antimicrobial polymers
CN104957168A (en) * 2015-02-13 2015-10-07 山东科技大学 Halamine-pyridine salt double-function group polysiloxane bactericide, and preparation method and application thereof
CN107880211A (en) * 2017-11-03 2018-04-06 浙江肯特催化材料科技有限公司 A kind of preparation method of the insoluble type quaternary ammonium salt of water
CN108641086A (en) * 2018-05-16 2018-10-12 山东交通学院 A kind of raw-silastic continuously containing quaternary ammonium salt and its synthesis and the application in preparing intrinsic quaternary antimildew and antibacterial fluid sealant
CN109293804A (en) * 2018-08-21 2019-02-01 南京理工大学 Selfreparing activeness and quietness composite material and preparation method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090311302A1 (en) * 2005-08-24 2009-12-17 Youngblood Jeffrey P Hydrophilized antimicrobial polymers
CN104957168A (en) * 2015-02-13 2015-10-07 山东科技大学 Halamine-pyridine salt double-function group polysiloxane bactericide, and preparation method and application thereof
CN107880211A (en) * 2017-11-03 2018-04-06 浙江肯特催化材料科技有限公司 A kind of preparation method of the insoluble type quaternary ammonium salt of water
CN108641086A (en) * 2018-05-16 2018-10-12 山东交通学院 A kind of raw-silastic continuously containing quaternary ammonium salt and its synthesis and the application in preparing intrinsic quaternary antimildew and antibacterial fluid sealant
CN109293804A (en) * 2018-08-21 2019-02-01 南京理工大学 Selfreparing activeness and quietness composite material and preparation method

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