CN109232834A - It is a kind of with anti-pollution-sterilization-release triple functions antibacterial polymer brush and preparation method thereof - Google Patents
It is a kind of with anti-pollution-sterilization-release triple functions antibacterial polymer brush and preparation method thereof Download PDFInfo
- Publication number
- CN109232834A CN109232834A CN201810871927.0A CN201810871927A CN109232834A CN 109232834 A CN109232834 A CN 109232834A CN 201810871927 A CN201810871927 A CN 201810871927A CN 109232834 A CN109232834 A CN 109232834A
- Authority
- CN
- China
- Prior art keywords
- polymer brush
- response type
- pollution
- sterilization
- brush
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
-
- 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
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
-
- 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
- C08F8/18—Introducing halogen atoms or halogen-containing groups
-
- 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
- C08F2438/00—Living radical polymerisation
- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a kind of preparation methods with anti-pollution-sterilization-release triple functions antibacterial polymer brush, comprising the following steps: 1) living radical initiator is grafted on substrate material surface;2) base material of graft initiator and stimuli responsive type monomer are subjected to polymerization reaction, obtain response type polymer brush;3) response type polymer brush and hydrophilic monomer are subjected to polymerization reaction, obtain hydrophilic response type polymer brush;4) hydrophilic response type polymer brush is grafted triclosan antimicrobial agent or silver nanoparticles loaded, obtains the antibacterial polymer brush.The polymer brush that the method for the present invention obtains has anti-pollution, sterilization, release triple functions, imparts the multi-functional of the long-acting anti-pollution of antimicrobial surface, efficient sterilizing and bacterium release, has widened its application field significantly.
Description
Technical field
The present invention relates to a kind of preparation technical fields of antimicrobial surface, and in particular to one kind has anti-pollution-sterilization-release three
The antibacterial polymer brush and preparation method thereof of weight function.
Background technique
Bacterium is widely present in nature and human production life environment, seriously affects the health and life of people
Safety.Bacterium infection and propagate be mainly bacterium attachment on the surface of the material and breeding process, in this course, bacterium is first
It first adheres on the surface of the material, cell biological film is then formed by extracellular matrix secretion, the formation of cell biological film can significantly
Bacterial antibiotic, fungicide and the resistivity of human immune system is improved therefore to be the key of bacterial-infection resisting
Prevent the formation of bacterial adhesion and cell biological film.
Polymer brush is a kind of fixed high density polymer strand on the surface of the material or on interface in one end, it has also become is adjusted
It controls surface nature and realizes one of the important means of surface-functionalized, it is excellent to have that preparation method is easy, structure controllability is strong etc.
Gesture presents broad prospect of application in fields such as surface and interface modification, nano-hybrid material, biological medicines, is antimicrobial surface
Preparation is also provided that huge potentiality and space.
Traditional antimicrobial surface mainly has " actively sterilizing ", " long-acting anti-pollution ", " anti-pollution-sterilization " and " sterilization-release "
Four kinds, but there are some disadvantages in them.Specifically, it " actively sterilizes " although surface can kill bacterium, that kills is thin
Bacterium can not remove, and shield fungicide, later period bactericidal potency is caused to substantially reduce;" long-acting anti-pollution " surface can be glued in prolonged application
Attached bacteria, and bacterium can not be desorbed;" anti-pollution-sterilization " and " sterilization-release " although surface have dual function, the former
There are still inevitably bacterial adhesion, the latter needs frequent regeneration, these disadvantages have seriously affected the application of function antimicrobial surface
Efficiency and field.
Chinese invention patent CN107759104A discloses a kind of quaternary ammonium polymer brush antibacterial material based on Si-ATRP method
Material and preparation method thereof, specific steps are as follows: 1) surface modification is had into the base material of hydroxyl and/or amino and bromo isobutyl acylbromide
Reaction, obtains the base material for being fixed with initiator;2) in inert atmosphere and water, by above-mentioned base material and acrylic amide
Monomer carries out polymerization reaction under the action of catalyst system, obtains the base material for having polymer brush to surface;3) surface is had poly-
The base material for closing object brush carries out amide degradation reaction, is then soaked in the organic solution of iodomethane and carries out quaternization reaction,
Washing, it is dry, obtain quaternary ammonium polymer brush anti-biotic material.
The obtained polymer brush of foregoing invention method only has the function of antibacterial, has a single function, application range is narrow, and this hair
The multifunctional polymer brush that bright method obtains can make antimicrobial surface while have anti-pollution-sterilization-release triple functions, have anti-
Dirt-sterilization-release triple functions antimicrobial surface will be current research tendency.
Summary of the invention
The object of the present invention is to provide one kind to have long-acting anti-bacterial attachment, can be killed and release again after bacterial adhesion
Put the antibacterial polymer brush and preparation method thereof of dead bacterium triple functions.
A kind of preparation method with anti-pollution-sterilization-release triple functions antibacterial polymer brush, comprising the following steps:
Step 1: living radical initiator is grafted on substrate material surface;
Step 2: the base material and stimuli responsive type monomer that step 1 is obtained carry out polymerization reaction, and it is poly- to obtain response type
Close object brush;
Step 3: the response type polymer brush and hydrophilic monomer that step 2 is obtained carry out polymerization reaction, obtain hydrophilic sound
Answer type polymer brush;
Step: 4: the grafting triclosan antimicrobial agent of hydrophilic response type polymer brush or load silver nanoparticle that step 3 is obtained
Grain obtains the antibacterial polymer brush.
The method of the present invention successively causes response type monomer and hydrophilic by using different reaction systems on base material
Property monomer, then be grafted small molecule antibacterial agent TCS or in-situ silver-carried, realize the technology of preparing of multifunctional antibiotic polymer brush.This hair
When responsive polymer chain on bright obtained multifunctional antibiotic polymer brush crimps, hydrophilic chain exposure therein, high-hydrophilic
Realize long-acting anti-bacterial attachment in surface;And under environmental stimuli, the responsive polymer chain-unfolding on polymer brush, chain structure can be made
Bacterium is desorbed in the stretching force as caused by variation, assigns the function of its bacterium release;In addition, obtained polymer brush surface is negative
The small molecule antibacterial agent TCS or Nano silver grain of load are able to achieve efficient sterilization again, assign the function of its sterilization.
The specific steps of the step 1 are as follows: base material oxygen plasma surface processor is handled into 2-3min, then will
It handles obtained base material and is placed in the toluene solution dissolved with living radical initiator and impregnate 20-28h.
The polymerization reaction of the step 2 and step 3 is atom transfer radical polymerization (ATRP) reaction, and specific steps are such as
Under:
Step 2: under nitrogen protection, after mixing by stimuli responsive type monomer, ligand and solvent, being added equipped with catalysis
In the container of the base material of agent and surface grafting ATRP initiator, 6-36h is reacted under anaerobic and obtains response type polymerization
Object brush;
Step 3: under nitrogen protection, after mixing by hydrophilic monomer, ligand and solvent, be added equipped with catalyst and
In the container of the response type polymer brush, 6-36h is reacted under anaerobic, obtains the hydrophilic response type polymer brush;
The catalyst is CuCl, CuBr, CuCl/CuCl2、CuBr/CuBr2;
The ligand is Me6TREN,PMDETA,BPy;
Monomer, ligand and the catalyst quality ratio is 30-150:0.5-3:1;
The solvent is the mixing of the NaBr of the mixed liquor of the methanol that volume ratio is 1:1 and water, methanol and 0.53mol/L
The mixed liquor of liquid, the mixed liquor of trifluoroethanol and water or isopropanol and water;
The ATRP initiator is (the bromo- 2- methyl-prop monomethacryloxypropyl of 2-) trimethoxy silane, and structural formula is as follows:
The polymerization reaction of the step 2 and step 3 is Invertible ideal (RAFT) reaction, specific steps
It is as follows:
Step 2: by stimuli responsive type monomer, solvent, RAFT reagent and the base material mixing for being grafted radical initiator
Uniformly, it is warming up to 60-80 DEG C of reaction 6-36h, obtains the response type polymer brush;
Step 3: hydrophilic monomer, solvent, RAFT reagent and response type polymer brush being uniformly mixed, 60-80 is warming up to
DEG C reaction 6-36h, obtain the hydrophilic response type polymer brush;
The radical initiator is ACVA, and structural formula is as follows:
The RAFT reagent is CPADB, and structural formula is as follows:
The monomer, RAFT reagent, radical initiator mass ratio are 30-150:2-10:1.
The polymerization reaction of the step 2 and step 3 is that light-initiated transfer terminates polymerization reaction, the specific steps are as follows:
Step 2: under nitrogen protection, by stimuli responsive type monomer, solvent and be grafted radical initiator base material,
0.5-2h is reacted under the ultraviolet irradiation of 365nm, obtains the response type polymer brush;
Step 3: under nitrogen protection, hydrophilic monomer, solvent and response type polymer brush being uniformly mixed, in 365nm
Ultraviolet irradiation under react 0.5-2h, obtain the hydrophilic response type polymer brush;
The photoinitiator is SBDC, and structural formula is as follows:
The monomer, photoinitiator mass ratio are 30-150:1.
Base material described in step 1 is silicon wafer, sheet glass, sheet metal, polyurethane surface, silastic surface or poly- third
Alkene surface.
Response type monomer described in step 2 is n-isopropyl acrylamide, methacrylic acid or dimethyl-(4- ethylene
Phenyl) ammonium propane sulfonic acid inner salt.
Hydrophilic monomer described in step 3 is hydroxyethyl methacrylate, N- hydroxyethyl acrylamide, sulfobetaines
Methacrylate, carboxybetaine methyl methacrylate, any one in polyethylene glycol methacrylate-styrene polymer.Step 4
Described in grafting triclosan antimicrobial agent the step of are as follows: the polymer brush that step (1) obtains is placed in the nothing of the agent containing triclosan antimicrobial
In water dichloromethane solution, 12h is reacted at room temperature, obtains the multifunctional antibiotic polymer brush;
The triclosan antimicrobial agent the preparation method comprises the following steps: TCS is dissolved in triethylamine and anhydrous methylene chloride, then will mix
Conjunction liquid is added to anhydrous methylene chloride and makees in the oxalyl chloride of solvent, and 2h is reacted at 0 DEG C, and after reacting 2h at room temperature, revolving purification is obtained
To triclosan antimicrobial agent.
The step of silver nanoparticles loaded described in step (2) are as follows: polymer brush is immersed in the AgNO of 0.1mol/L3It is molten
In liquid, the NaBH of 0.1mol/L is added4Solution infiltrates 6-24h, obtains the multifunctional antibiotic polymer brush.
The present invention also provides a kind of with anti-pollution-sterilization-release triple functions antibacterial polymer brush, and the antibacterial is poly-
Close object brush be prepared by the above method, the antibacterial polymer brush with a thickness of 10-150nm.The present invention is poly- by control
In the reaction time for closing reaction, the thickness of obtained antibacterial polymer brush can be accurately controlled, to meet the needs of different.
Compared with the prior art, the present invention has the following beneficial effects:
(1) the method for the present invention uses different reaction systems, successively causes response type monomer and hydrophilic on base material
Property monomer, then be grafted small molecule antibacterial agent TCS or in-situ silver-carried, be prepared for that there is anti-pollution, sterilization, the antibacterial for discharging triple functions
Polymer brush imparts the multi-functional of the long-acting anti-pollution of antimicrobial surface, efficient sterilizing and bacterium release, has widened it significantly and answered
Use field;
(2) the method for the present invention is simple, and safety is good, and the structure of constructed polymer brush can be accurately controlled, response
Sensitivity is high.
Detailed description of the invention
Fig. 1 is the structural representation with anti-pollution-sterilization-release triple functions antibacterial polymer brush that the present invention obtains
Figure;
Fig. 2 is that the brush of poly (DVBAPS-b-HEAA-g-TCS) obtained in embodiment 1 recycles Escherichia coli 3
The statistical chart of fluorescent image, bacterial number and sterilizing rate release rate.
Specific embodiment
The invention is further illustrated by the examples, but the present invention is not limited by following embodiment.
Embodiment 1
(1) silicon wafer oxygen plasma surface processor is handled into 2min, then the silicon wafer that processing obtains is placed in dissolved with (2-
Bromo- 2- methyl-prop monomethacryloxypropyl) trimethoxy silane toluene solution in impregnate for 24 hours;
(2) 2 clean test tubes, number test tube 1 and test tube 2 are taken, sequentially adds 0.35g DVBAPS, 1.5mL in test tube 1
Trifluoroethanol, 1.5mL deionized water, 7 μ L ligand Me6TREN;7mgCuBr and 2 step (1) is sequentially added in test tube 2 to obtain
Silicon wafer;Two test tubes remove oxygen and filling nitrogen 3 times, then after bulging nitrogen 30min, the liquid in test tube 1 is retracted to test tube 2 with syringe
In, again remove oxygen and filling nitrogen 3 times, test tube 2 is reacted for 24 hours in 25 DEG C of constant temperature oscillation box, after reaction successively in salt water, go
It is cleaned by ultrasonic respectively in ionized water 2 times, is dried with nitrogen, obtains poly DVBAPS brush;
(3) 2 clean test tubes, number test tube 1 and test tube 2 are taken, 0.5g HEAA, 1.5mL first are sequentially added in test tube 1
Alcohol, the NaBr solution of the 0.53mol/L of 1.5mL, 7 μ L ligand Me6TREN;7mgCuBr and 2 poly is sequentially added in test tube 2
DVBAPS brush;Two test tubes remove oxygen and filling nitrogen 3 times, then after bulging nitrogen 30min, the liquid in test tube 1 is retracted to examination with syringe
In pipe 2, again remove oxygen and filling nitrogen 3 times, test tube 2 is reacted for 24 hours in 25 DEG C of constant temperature oscillation box, after reaction in ethyl alcohol, go
Successively it is cleaned by ultrasonic in ionized water 2 times, is dried with nitrogen, obtains the double-deck brush of poly (DVBAPS-b-HEAA), it is spare;
(4) it takes 2.9g TCS to be added in the mixed solution of 2mL triethylamine and 10mL anhydrous methylene chloride, then gained is mixed
It closes drop to enter in the 5mL anhydrous methylene chloride of the oxalyl chloride containing 1.9g, 2h is reacted at 0 DEG C, then react 2h at room temperature, reaction knot
Shu Hou, revolving purification obtain product;Poly (DVBAPS-b-HEAA) is brushed in the anhydrous methylene chloride solution containing above-mentioned product again
In react 12h under nitrogen protection, successively cleaned in methylene chloride, ethyl alcohol, deionized water 2 times after reaction, nitrogen is blown
It is dry, obtain poly (DVBAPS-b-HEAA-g-TCS) brush.
Obtained poly (DVBAPS-b-HEAA-g-TCS) brush is placed in certain density bacterial solution (Escherichia coli OD
=0.1;Staphylococcus aureus OD=0.05) in culture, per being shot on this polymer brush using inverted fluorescence microscope for 24 hours
Bacterium situation (dead bacterium+viable bacteria) quantitatively calculates the density of bacterium.Quantity to bacterium reaches~106cells/cm2When, use 1M/L
Salt water desorption, retrieve clean antimicrobial surface, with this recycle carry bacterium, realize the three of long-acting " anti-pollution-sterilization-release "
Weight function.
Obtained poly (DVBAPS-b-HEAA-g-TCS) brush is for Escherichia coli 3 fluorescent images recycled, bacteriums
The statistical chart of quantity and sterilizing rate release rate is shown in Fig. 2.
As shown in Fig. 2, wherein a) indicating poly (DVBAPS-b-HEAA-g-TCS) brush for three circulations of Escherichia coli
The bacterial fluorescence figure (green represents viable bacteria, and red represents dead bacterium) of (120h/ circulation), it can be found that using 1M/L in each circulation
NaCl response desorption after, the bacterium on surface all has a large amount of reduction;B) what is indicated is that three bacterial numbers recycled are close
Degree, after third recycles (360h), density is still~106cells/cm2, have the function of excellent anti-adhesive;C) 3 are indicated
The sterilizing rate and desorption rate of a circulation bacterium, efficiency show that it is discharged with excellent sterilization and dead bacterium 90% or more
Function.
It is similar for the antibacterial process of remaining responsiveness monomer, it is only necessary to response (stimulation) item of the corresponding responsiveness monomer
Part.
Embodiment 2
(1) silicon wafer oxygen plasma surface processor is handled into 2min, then the silicon wafer that processing obtains is placed in dissolved with (2-
Bromo- 2- methyl-prop monomethacryloxypropyl) trimethoxy silane toluene solution in impregnate for 24 hours;
(2) 2 clean test tubes, number test tube 1 and test tube 2 are taken, 0.5g NIPAM, 1.5mL first are sequentially added in test tube 1
Alcohol, 1.5mL deionized water, 33 μ L ligand PMDETA;The silicon that 13mgCuBr and 2 step (1) obtains is sequentially added in test tube 2
Piece;Two test tubes remove oxygen and filling nitrogen 3 times, then after bulging nitrogen 30min, the liquid in test tube 1 is retracted in test tube 2 with syringe,
Again remove oxygen and filling nitrogen 3 times, test tube 2 reacts 12h in 25 DEG C of constant temperature oscillation box, after reaction successively in methanol, ethyl alcohol, go
Respectively it is cleaned by ultrasonic in ionized water 2 times, is dried with nitrogen, obtains polyNIPAM brush;
(3) 2 clean test tubes, number test tube 1 and test tube 2 are taken, 0.5g HEAA, 1.5mL first are sequentially added in test tube 1
Alcohol, 1.5mL deionized water, 7 μ L ligand Me6TREN;7mgCuBr and 2 polyNIPAM brush is sequentially added in test tube 2.Two examinations
Guan Jun is removed oxygen and filling nitrogen 3 times, then after bulging nitrogen 30min, the liquid in test tube 1 is retracted in test tube 2 with syringe, deoxygenation is filled again
Nitrogen 3 times, test tube 2 reacts for 24 hours in 25 DEG C of constant temperature oscillation box, and successively ultrasound is clear in ethyl alcohol, deionized water after reaction
It washes 2 times, is dried with nitrogen, obtain the double-deck brush of poly (NIPAM-b-HEAA), it is spare;
(4) it takes 2.9gTCS to be added in the mixed solution of 2mL triethylamine and 10mL anhydrous methylene chloride, then this is mixed
Liquid in the 5mL anhydrous methylene chloride of the 1.9g containing oxalyl chloride, reacts 2h, then react 2h at room temperature, reaction terminates dropwise at 0 DEG C
Afterwards, revolving purification obtains product;Again by poly (NIPAM-b-HEAA) brush in the anhydrous methylene chloride solution containing above-mentioned product
12h is reacted under nitrogen protection, is successively cleaned 2 times, is dried with nitrogen in methylene chloride, ethyl alcohol, deionized water after reaction,
Obtain poly (NIPAM-b-HEAA-g-TCS) brush.
Embodiment 3
(1) silicon wafer oxygen plasma surface processor is handled into 2min, then the silicon wafer that processing obtains is placed in dissolved with (2-
Bromo- 2- methyl-prop monomethacryloxypropyl) trimethoxy silane toluene solution in impregnate for 24 hours;
(2) 2 clean test tubes, number test tube 1 and test tube 2 are taken, 0.54gMAA is sequentially added in test tube 1 and 3.0mL is gone
Ionized water;43mg ligand Bpy, 11mg CuBr/CuBr are sequentially added in test tube 22(m:m=1:1) mixture and 2 steps
(1) silicon wafer obtained;Two test tubes remove oxygen and filling nitrogen 3 times, then after bulging nitrogen 30min, are extracted out the liquid in test tube 1 with syringe
Into test tube 2, remove oxygen and filling nitrogen 3 times again, test tube 2 reacts 12h in 25 DEG C of constant temperature oscillation box, after reaction successively in second
Respectively it is cleaned by ultrasonic in alcohol, deionized water 2 times, is dried with nitrogen, obtains polyMAA brush;
(3) 2 clean test tubes, number test tube 1 and test tube 2 are taken, 0.5g HEAA, 1.5mL first are sequentially added in test tube 1
Alcohol, 1.5mL deionized water, 7 μ L ligand Me6TREN;7mgCuBr and 2 polyMAA brush is sequentially added in test tube 2;Two test tubes
It removes oxygen and filling nitrogen 3 times, then after bulging nitrogen 30min, the liquid in test tube 1 is retracted in test tube 2 with syringe, remove oxygen and filling nitrogen again
3 times, test tube 2 reacts for 24 hours in 25 DEG C of constant temperature oscillation box, is successively cleaned by ultrasonic 2 in ethyl alcohol, deionized water after reaction
It is secondary, it is dried with nitrogen, obtains the double-deck brush of poly (MAA-b-HEAA), it is spare;
(4) it takes 2.9gTCS to be added in the mixed solution of 2mL triethylamine and 10mL anhydrous methylene chloride, then this is mixed
Drop enters in the 5mL anhydrous methylene chloride of the 1.9g containing oxalyl chloride, 2h is reacted at 0 DEG C, then react 2h at room temperature, reaction terminates
Revolving purification afterwards obtains product;Again by poly (MAA--b-HEAA) brush in the anhydrous methylene chloride solution containing above-mentioned product
12h is reacted under nitrogen protection, is successively cleaned 2 times, is dried with nitrogen in methylene chloride, ethyl alcohol, deionized water after reaction, obtains
It is brushed to poly (MAA-b-HEAA-g-TCS).
Embodiment 4
(1) silicon wafer oxygen plasma surface processor is handled into 2min, then the silicon wafer that processing obtains is placed in dissolved with (2-
Bromo- 2- methyl-prop monomethacryloxypropyl) trimethoxy silane toluene solution in impregnate for 24 hours;
(2) 2 clean test tubes, number test tube 1 and test tube 2 are taken, sequentially adds 0.35g DVBAPS, 1.5mL in test tube 1
Trifluoroethanol, 1.5mL deionized water, 7 μ L ligand Me6TREN sequentially adds 7mgCuBr and 2 step (1) in test tube 2 and obtains
Silicon wafer;Two test tubes remove oxygen and filling nitrogen 3 times, then after bulging nitrogen 30min, the liquid in test tube 1 is retracted to test tube 2 with syringe
In, again remove oxygen and filling nitrogen 3 times, test tube 2 reacts for 24 hours in 25 DEG C of constant temperature oscillation box, after reaction successively salt water, go from
Respectively it is cleaned by ultrasonic in sub- water 2 times, is dried with nitrogen, obtains polyDVBAPS brush;
(3) 2 clean test tubes, number test tube 1 and test tube 2 are taken, sequentially adds 0.9g POEGMA, 1.5mL in test tube 1
Methanol, 1.5mL 0.53mol/L NaBr solution;23mg ligand Bpy, 5mgCuBr and 2 are sequentially added in test tube 2
PolyDVBAPS brush;Two test tubes remove oxygen and filling nitrogen 3 times, then after bulging nitrogen 30min, are extracted out the liquid in test tube 1 with syringe
Into test tube 2, again remove oxygen and filling nitrogen 3 times, test tube 2 reacts for 24 hours in 25 DEG C of constant temperature oscillation box, after reaction ethyl alcohol,
Successively it is cleaned by ultrasonic in deionized water 2 times, is dried with nitrogen, obtains the double-deck brush of poly (DVBAPS-b-POEGMA), it is spare;
(4) it takes 2.9gTCS to be added in the mixed solution of 2mL triethylamine and 10mL anhydrous methylene chloride, then this is mixed
Drop enters in the 5mL anhydrous methylene chloride of the 1.9g containing oxalyl chloride, 2h is reacted at 0 DEG C, then react 2h at room temperature, reaction terminates
Revolving purification afterwards obtains product;Poly (DVBAPS-b-POEGMA) is brushed in the anhydrous methylene chloride solution containing above-mentioned product again
In react 12h under nitrogen protection, successively cleaned in methylene chloride, ethyl alcohol, deionized water 2 times after reaction, nitrogen is blown
It is dry, obtain polymer brush poly (DVBAPS-b-POEGMA-g-TCS).
Embodiment 5
(1) silicon wafer oxygen plasma surface processor is handled into 2min, then the silicon wafer that processing obtains is placed in dissolved with light
It is impregnated for 24 hours in the toluene solution of initiator SBDC;
(2) 1 clean test tube is taken, the NaBr solution and step of the 0.53mol/L of 0.35gDVBAPS, 3.5mL are sequentially added
Suddenly the silicon wafer that (1) obtains removes oxygen and filling nitrogen 3 times, drum nitrogen 30min;1h is reacted under the ultraviolet lamp of 365nm, after reaction according to
It is secondary to be respectively cleaned by ultrasonic in salt water, deionized water 2 times, it is dried with nitrogen, obtains polyDVBAPS brush;
(3) take 1 clean test tube, sequentially add 0.5g HEAA, 1.5mL methanol, 1.5mL deionized water and
PolyDVBAPS brush, reacts 45min, after reaction in methanol, ethyl alcohol, deionized water successively under the ultraviolet lamp of 365nm
Ultrasonic cleaning 2 times, is dried with nitrogen, and obtains the double-deck brush of poly (DVBAPS-b-HEAA), spare;
(4) above-mentioned poly (DVBAPS-b-HEAA) brush is immersed in the AgNO of 0.1mol/L3In solution, then it is slowly added dropwise
The NaBH of 0.1mol/L4Solution 10mL, infiltrates 12h, and in-situ reducing obtains poly (DVBAPS-b-HEAA)@at Nano silver grain
Ag compound system.
Embodiment 6
(1) silicon wafer oxygen plasma surface processor is handled into 2min, then will the obtained silicon wafer of processing be placed in dissolved with
It is impregnated for 24 hours in the toluene solution of ACVA;
(2) 1 clean test tube is taken, 5.3mL MAA, 14.5mL ethyl alcohol, 175mg CPADB and step (1) are sequentially added
Obtained silicon wafer, isothermal reaction for 24 hours, is successively respectively cleaned by ultrasonic 2 times in ethyl alcohol, deionized water after reaction at 70 DEG C,
It is dried with nitrogen, obtains polyMAA brush;
(3) 1 clean test tube is taken, 0.5gHEAA, 15.5mL methanol, 175mg CPADB and polyMAA are sequentially added
Brush, isothermal reaction for 24 hours, is successively respectively cleaned by ultrasonic 2 times, nitrogen in methanol, ethyl alcohol, deionized water after reaction at 70 DEG C
Drying obtains the double-deck brush of poly (MAA-b-HEAA), spare;
(4) it takes 2.9gTCS to be added in the mixed solution of 2mL triethylamine and 10mL anhydrous methylene chloride, then this is mixed
Drop enters in the 5mL anhydrous methylene chloride of the 1.9g containing oxalyl chloride, 2h is reacted at 0 DEG C, then react 2h at room temperature, reaction terminates
Revolving purification afterwards obtains product;Poly (MAA-b-HEAA) is brushed in the anhydrous methylene chloride solution containing above-mentioned product in nitrogen again
12h is reacted under gas shielded, is successively cleaned 2 times, is dried with nitrogen in methylene chloride, ethyl alcohol, deionized water after reaction, obtains
It is grafted the polymer brush poly (MAA-b-HEAA-g-TCS) of small molecule antibacterial agent.
Claims (10)
1. a kind of preparation method with anti-pollution-sterilization-release triple functions antibacterial polymer brush, comprising the following steps:
Step 1: living radical initiator is grafted on substrate material surface;
Step 2: the base material and stimuli responsive type monomer that step 1 is obtained carry out polymerization reaction, obtain response type polymer
Brush;
Step 3: the response type polymer brush and hydrophilic monomer that step 2 is obtained carry out polymerization reaction, obtain hydrophilic response type
Polymer brush;
Step: 4: the hydrophilic response type polymer brush grafting triclosan antimicrobial agent that step 3 is obtained or silver nanoparticles loaded obtain
To the antibacterial polymer brush.
2. there is the preparation method of anti-pollution-sterilization-release triple functions antibacterial polymer brush as described in claim 1,
It is characterized in that, the specific steps of the step 1 are as follows: base material oxygen plasma surface processor is handled into 2-3min, then
The base material that processing obtains is placed in the toluene solution dissolved with living radical initiator and impregnates 22-26h.
3. there is the preparation method of anti-pollution-sterilization-release triple functions antibacterial polymer brush as described in claim 1,
It is characterized in that, the polymerization reaction of the step 2 and step 3 is atom transition free radical polymerization reaction, the specific steps are as follows:
Step 2: under nitrogen protection, after mixing by stimuli responsive type monomer, ligand and solvent, be added equipped with catalyst and
In the container of the base material of surface grafting ATRP initiator, 6-36h is reacted under anaerobic and obtains response type polymer brush;
Step 3: under nitrogen protection, after mixing by hydrophilic monomer, ligand and solvent, being added equipped with catalyst and described
In the container of response type polymer brush, 6-36h is reacted under anaerobic, obtains the hydrophilic response type polymer brush.
4. there is the preparation method of anti-pollution-sterilization-release triple functions antibacterial polymer brush as described in claim 1,
It is characterized in that, the polymerization reaction of the step 2 and step 3 is Invertible ideal reaction, the specific steps are as follows:
Step 2: the base material of stimuli responsive type monomer, solvent, RAFT reagent and grafting radical initiator is uniformly mixed,
It is warming up to 60-80 DEG C of reaction 6-36h, obtains the response type polymer brush;
Step 3: hydrophilic monomer, solvent, RAFT reagent and response type polymer brush being uniformly mixed, are warming up to 60-80 DEG C instead
6-36h is answered, the hydrophilic response type polymer brush is obtained.
5. there is the preparation method of anti-pollution-sterilization-release triple functions antibacterial polymer brush as described in claim 1,
It is characterized in that, the polymerization reaction of the step 2 and step 3 is that light-initiated transfer terminates polymerization reaction, the specific steps are as follows:
Step 2: under nitrogen protection, by stimuli responsive type monomer, solvent and be grafted radical initiator base material, in
0.5-2h is reacted under the ultraviolet irradiation of 365nm, obtains the response type polymer brush;
Step 3: under nitrogen protection, hydrophilic monomer, solvent and response type polymer brush being uniformly mixed, in the purple of 365nm
0.5-2h is reacted under external exposure, obtains the hydrophilic response type polymer brush.
6. the preparation as described in any one in claim 1-5 with anti-pollution-sterilization-release triple functions antibacterial polymer brush
Method, which is characterized in that the base material is silicon wafer, sheet glass, sheet metal, polyurethane surface, silastic surface or poly-
Propylene surface.
7. the preparation as described in any one in claim 1-5 with anti-pollution-sterilization-release triple functions antibacterial polymer brush
Method, which is characterized in that the response type monomer is n-isopropyl acrylamide, methacrylic acid or dimethyl-(4- ethylene
Phenyl) ammonium propane sulfonic acid inner salt.
8. the preparation as described in any one in claim 1-5 with anti-pollution-sterilization-release triple functions antibacterial polymer brush
Method, which is characterized in that the hydrophilic monomer is hydroxyethyl methacrylate, N- hydroxyethyl acrylamide, sulfobetaines
Alkali methacrylate, carboxybetaine methyl methacrylate, any one in polyethylene glycol methacrylate-styrene polymer.
9. a kind of with anti-pollution-sterilization-release triple functions antibacterial polymer brush, which is characterized in that the antibacterial polymer
Brush method as described in any one of claim 1~8 is prepared.
10. having anti-pollution-sterilization-release triple functions antibacterial polymer brush as claimed in claim 9, which is characterized in that
The antibacterial polymer brush with a thickness of 10-150nm.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810871927.0A CN109232834A (en) | 2018-08-02 | 2018-08-02 | It is a kind of with anti-pollution-sterilization-release triple functions antibacterial polymer brush and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810871927.0A CN109232834A (en) | 2018-08-02 | 2018-08-02 | It is a kind of with anti-pollution-sterilization-release triple functions antibacterial polymer brush and preparation method thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
CN109232834A true CN109232834A (en) | 2019-01-18 |
Family
ID=65072878
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810871927.0A Pending CN109232834A (en) | 2018-08-02 | 2018-08-02 | It is a kind of with anti-pollution-sterilization-release triple functions antibacterial polymer brush and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109232834A (en) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110330658A (en) * | 2019-06-14 | 2019-10-15 | 浙江工业大学 | A kind of sterilization, low bacterial adhesion, the anti-bacterial hydrogel of bacterium release and its preparation method and application |
CN110484062A (en) * | 2019-08-29 | 2019-11-22 | 浙江工业大学 | It is a kind of to construct anti-pollution-sterilization-release surface coating method and products thereof using dopamine |
CN110511624A (en) * | 2019-08-26 | 2019-11-29 | 浙江工业大学 | A kind of preparation method and products thereof with sterilization and bacterium release action coating |
CN110628071A (en) * | 2019-09-25 | 2019-12-31 | 嘉兴学院 | Antibacterial degradable polymer and preparation method and application thereof |
CN111004360A (en) * | 2019-12-20 | 2020-04-14 | 佛山科学技术学院 | Double-layer multifunctional polymer brush surface and preparation method thereof |
CN111533861A (en) * | 2020-05-08 | 2020-08-14 | 浙江工业大学 | Solid surface polymer double-layer brush material for adsorbing heavy metal ions and preparation method and application thereof |
CN112048223A (en) * | 2020-08-31 | 2020-12-08 | 浙江工业大学 | Anti-fouling, sterilizing and releasing multifunctional response antibacterial surface and preparation method thereof |
CN112048224A (en) * | 2020-08-31 | 2020-12-08 | 浙江工业大学 | Antibacterial surface with dual functions of sterilization and release and preparation method thereof |
CN112390951A (en) * | 2020-10-14 | 2021-02-23 | 浙江工业大学 | Preparation method of oxidation-responsive surface polythioether polymer brush material |
CN113082300A (en) * | 2021-04-06 | 2021-07-09 | 西南交通大学 | Antibacterial and anticoagulant coating, preparation method and application thereof |
CN114788897A (en) * | 2021-01-25 | 2022-07-26 | 苏州林华医疗器械股份有限公司 | Preparation method and application of antibacterial joint |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014194268A1 (en) * | 2013-05-30 | 2014-12-04 | The University Of Akron | Switchable antimicrobial and antifouling carboxybetaine-based hydrogels |
CN107868260A (en) * | 2017-10-20 | 2018-04-03 | 浙江工业大学 | A kind of preparation method of low bacterial adhesion, sterilization and reproducible novel hydrogels |
-
2018
- 2018-08-02 CN CN201810871927.0A patent/CN109232834A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014194268A1 (en) * | 2013-05-30 | 2014-12-04 | The University Of Akron | Switchable antimicrobial and antifouling carboxybetaine-based hydrogels |
CN107868260A (en) * | 2017-10-20 | 2018-04-03 | 浙江工业大学 | A kind of preparation method of low bacterial adhesion, sterilization and reproducible novel hydrogels |
Non-Patent Citations (3)
Title |
---|
BOZHEN WU ET AL.: "Salt-Induced Regenerative Surface for Bacteria Killing and Release", 《LANGMUIR》 * |
HAI-XIA WU ET AL.: "Highly Efficient Antibacterial Surface Grafted with a Triclosan-Decorated Poly(N Hydroxyethylacrylamide) Brush", 《ACS APPL. MATER. INTERFACES》 * |
左彦: "具有抗细菌黏附和杀菌性能的高分子材料研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110330658A (en) * | 2019-06-14 | 2019-10-15 | 浙江工业大学 | A kind of sterilization, low bacterial adhesion, the anti-bacterial hydrogel of bacterium release and its preparation method and application |
CN110330658B (en) * | 2019-06-14 | 2021-06-22 | 浙江工业大学 | Antibacterial hydrogel with functions of sterilization, low bacterial adhesion and bacterial release and preparation method and application thereof |
CN110511624A (en) * | 2019-08-26 | 2019-11-29 | 浙江工业大学 | A kind of preparation method and products thereof with sterilization and bacterium release action coating |
CN110511624B (en) * | 2019-08-26 | 2021-03-23 | 浙江工业大学 | Preparation method of coating with sterilization and bacterial release effects and product thereof |
CN110484062A (en) * | 2019-08-29 | 2019-11-22 | 浙江工业大学 | It is a kind of to construct anti-pollution-sterilization-release surface coating method and products thereof using dopamine |
CN110484062B (en) * | 2019-08-29 | 2021-04-06 | 浙江工业大学 | Method for constructing anti-fouling, sterilizing and releasing surface coating by utilizing dopamine and product thereof |
CN110628071A (en) * | 2019-09-25 | 2019-12-31 | 嘉兴学院 | Antibacterial degradable polymer and preparation method and application thereof |
CN110628071B (en) * | 2019-09-25 | 2022-04-29 | 嘉兴学院 | Antibacterial degradable polymer and preparation method and application thereof |
CN111004360A (en) * | 2019-12-20 | 2020-04-14 | 佛山科学技术学院 | Double-layer multifunctional polymer brush surface and preparation method thereof |
CN111533861A (en) * | 2020-05-08 | 2020-08-14 | 浙江工业大学 | Solid surface polymer double-layer brush material for adsorbing heavy metal ions and preparation method and application thereof |
CN112048224A (en) * | 2020-08-31 | 2020-12-08 | 浙江工业大学 | Antibacterial surface with dual functions of sterilization and release and preparation method thereof |
CN112048223A (en) * | 2020-08-31 | 2020-12-08 | 浙江工业大学 | Anti-fouling, sterilizing and releasing multifunctional response antibacterial surface and preparation method thereof |
CN112048223B (en) * | 2020-08-31 | 2021-10-08 | 浙江工业大学 | Anti-fouling, sterilizing and releasing multifunctional response antibacterial surface and preparation method thereof |
CN112048224B (en) * | 2020-08-31 | 2021-10-08 | 浙江工业大学 | Antibacterial surface with dual functions of sterilization and release and preparation method thereof |
CN112390951A (en) * | 2020-10-14 | 2021-02-23 | 浙江工业大学 | Preparation method of oxidation-responsive surface polythioether polymer brush material |
CN112390951B (en) * | 2020-10-14 | 2022-07-15 | 浙江工业大学 | Preparation method of surface polythioether polymer brush material with oxidation responsiveness |
CN114788897A (en) * | 2021-01-25 | 2022-07-26 | 苏州林华医疗器械股份有限公司 | Preparation method and application of antibacterial joint |
CN113082300A (en) * | 2021-04-06 | 2021-07-09 | 西南交通大学 | Antibacterial and anticoagulant coating, preparation method and application thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN109232834A (en) | It is a kind of with anti-pollution-sterilization-release triple functions antibacterial polymer brush and preparation method thereof | |
CN106565912B (en) | A kind of polyquaternium quasi polymer lotion antibacterial agent and its preparation method and application | |
Yao et al. | Antibacterial effect of surface-functionalized polypropylene hollow fiber membrane from surface-initiated atom transfer radical polymerization | |
WO2022041429A1 (en) | Anti-fouling gel particles containing rare earth/anti-fouling agent and preparation method therefor | |
CN102924860B (en) | Hydrogel in-situ hybrid nano silver composite material and preparation method thereof | |
Chang et al. | N-Halamine polymer from bipolymer to amphiphilic terpolymer with enhancement in antibacterial activity | |
CN104341542A (en) | Antimicrobial polymers and coatings | |
CN104672379A (en) | Multifunctional modified antifouling coating resin and preparation method and applications thereof | |
CN104479487A (en) | Biological antibacterial and antifouling low surface energy coating with surface micro-structure and preparation method of biological antibacterial and antifouling low surface energy coating | |
CN110862680B (en) | Preparation method of fluorine-containing polyacrylic acid copolymer antibacterial composite material, obtained product and application | |
CN107868260B (en) | Preparation method of low-bacterial-adhesion, bactericidal and renewable hydrogel | |
Li et al. | Synthesis of cationic acrylate copolyvidone-iodine nanoparticles with double active centers and their antibacterial application | |
Wang et al. | Antimicrobial cationic acrylate-based hybrid coatings against microorganism contamination | |
Liang et al. | Salt-responsive polyzwitterion brushes conjugated with silver nanoparticles: Preparation and dual antimicrobial/release properties | |
Lee et al. | Ultrasonic fabrication of flexible antibacterial ZnO nanopillar array film | |
CN108057348A (en) | A kind of hydrophily sterilizing dye reverse osmosis membrane and its preparation method | |
CN107759104A (en) | A kind of quaternary ammonium polymer brush anti-biotic material based on Si ATRP methods and preparation method thereof | |
CN113797399B (en) | Use of non-releasing antimicrobial adhesion coating in antimicrobial medical devices | |
CN109942751A (en) | A kind of preparation method of plastics anti-biotic material | |
Chen et al. | Cooperative enhancement of fungal repelling performance by surface photografting of stereochemical bi-molecules | |
CN103483480A (en) | Artificial cell membrane materials applied to photoinduction stem grafting and synthesis method thereof | |
CN104628974B (en) | A kind of amphipathic copolymer and preparation method thereof assigning membrane material pH responses | |
EP1268580A1 (en) | Microbicidal coatings containing acrylo-substituted alkylsulphonic acid polymers | |
CN109134715B (en) | Preparation method of antifouling, bactericidal and reproducible long-acting antibacterial mixed polymer brush | |
CN109134754B (en) | Antibacterial micro-nano particles with adhesion function and preparation method and application thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190118 |
|
RJ01 | Rejection of invention patent application after publication |