CN106674512B - The method of open loop method building photocatalysis antibacterial stain resistant material - Google Patents
The method of open loop method building photocatalysis antibacterial stain resistant material Download PDFInfo
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- CN106674512B CN106674512B CN201611205203.XA CN201611205203A CN106674512B CN 106674512 B CN106674512 B CN 106674512B CN 201611205203 A CN201611205203 A CN 201611205203A CN 106674512 B CN106674512 B CN 106674512B
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- crosslinking agent
- resistant material
- stain resistant
- sulfone
- open loop
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Classifications
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- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
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Abstract
The method that open loop method constructs photocatalysis antibacterial stain resistant material, belongs to anti-bacterial and anti-fouling field of material technology.Anti-bacterial and anti-fouling field has light antibacterial, stain resistant material based on what epoxy, primaquine open loop base polymerization constructed.A kind of preparation method more particularly to photocatalysis antibacterial agent based on the building of open loop method and its application in antibacterial surface field.This method is simple and easy, easy to operate, synthesized polymer anti-bacterial and anti-fouling efficiency with higher.
Description
Technical field
The invention belongs to anti-bacterial and anti-fouling field of material technology, and in particular to the building of open loop method is a series of to be with photocatalysis antibacterial
Matrix, the material with high efficiency photocatalysis anti-bacterial and anti-fouling effect.
Background technique
Before the use of anti-biotic material can trace back to for a long time, the development of anti-biotic material has act in human social development
The status of sufficient weight is widely used in the production and living of people.Antibacterial agent includes natural antibacterial agent, and inorganic antiseptic is organic
Antibacterial agent.Some extracts of the natural antibacterial agent in animals and plants, such as allicin, chitosan, propolis etc..It is quilt earliest
The antibacterial agent that the mankind use.The chitosan in shrimp shell and crab shell is wherein derived from, contains active group in molecule, to many thin
Bacterium all shows good inhibiting effect.It is generally acknowledged that its Antibacterial Mechanism are as follows: positively charged-NH2 group in chitosan molecule
The anion binding come is dissociateed with silicic acid, phosphate contained in bacteria cell wall etc., hinders the activity of bacterium, then shell is poly-
Sugar is entered in bacterial cell by bacteria cell wall, is hindered transformation of the gene from DNA to RNA, be bred it can not.Naturally
Antibacterial agent is resourceful, from a wealth of sources, safety, nontoxic, but since its antibacterial duration is shorter, drug effect is not strong, limits
The mass market of natural antibacterial agent produces.With the raising of human research's technical level, the enhancing of environmental consciousness is natural anti-
Microbial inoculum will increasingly be taken seriously.Inorganic antiseptic be using with sterilization or bacteriostasis metal ion such as: silver, copper,
One kind antibacterial agent made from zinc, titanium etc..The inorganic antiseptic being wherein widely used mainly has: inorganic silver-series antibacterial agent, TiO2
Photocatalitic germicide, Zinc oxide whisker compound germicide and the other inorganic nano antiseptics etc. of series.Wherein silver-series antibacterial agent
The most extensively.Silver-series antibacterial agent can be divided into compound type and two class of carrier model.Boiling can be divided into according to the difference of carrier type again
Stone class antibacterial agent, clay class antibacterial agent, soluble glass antibacterial agent, silica gel antibacterial agent.Silver-series antibacterial agent has safety well
Property is i.e.: small toxicity, nonirritant, non-carcinogenesis, without teratogenesis etc., out except this ag system antimicrobial agent also have slow release it is good,
The advantages that broad spectrum antibacterial, good heat resistance and processability, to favor by researcher.Therefore inorganic silver antibacterial agent
It is current domestic most commonly used kind.Its mechanism of action is silver ion after being sustained out in carrier, with bacterium and fungal cell
In the sulfur-bearings such as-SH ,-NH2, ammonia functional group react, hinder protein synthesis and energy sources, destroy cell membrane or
The activity of enzyme in cellular plasm, to have antibacterial ability.There are many normal type of organic antibacterial agent, mainly have quaternary ammonium salts,
Alcohols, phenols, pyridines, isothiazolinone biguanides, organic amine etc..Organic antibacterial agent is to make bacterium by chemical reaction
Occur it is irreversible damage to play sterilization, anti-corrosion and it is mould proof the effects of.Organic antibacterial agent sterilizing power is strong, effect is good, and source is rich
Richness, but there are toxicity, safety is poor the deficiencies of, except so that microorganism is generated drug resistance, heat resistance poor, easy to migrate etc. for this
Problem.The organic surfactant antibacterial agent studied and used at present is usually cationic nitrogenous compound, such as quaternary ammonium father-in-law salt, pyridine
Nitrogenous heterocyclic father-in-law's salt such as father-in-law's salt, imidazolium salt, different Kui quinoline father-in-law's salt.Complex antimicrobials are to combine different types of antibacterial agent to make
At, by the synergistic effect and mutual supplement with each other's advantages between them, improve the performance and the scope of application of antibacterial agent, complex antimicrobials tool
There is the features such as cheap, dosage is few, stability is good, anti-microbial property is high.
However as the development in epoch, the drug resistance of bacterium constantly enhances in recent years, also lacks more effective at the same time
Antibacterials, develop new effective antibacterials have become it is extremely urgent.Although the variety classes having been reported in recent years
Antibacterials, but its can useful effect strain it is limited.In addition, the adherency proliferation of bacterium causes thin in medical instruments field
The superinfection of bacterium limits the use condition of medical instrument.The medicine relevant apparatus bacterium infection with human contact is known
Increase, infection rapidly become main clinical problem.Therefore, for clinical application, (such as suture, operation produce antifouling surface
Product and wound healing patch) to prevent from infecting in material wound or blood therefore, it is necessary to research and develop to currently common
Strain has the anti-biotic material of broad spectrum antibiotic activity, and antibiotic paint is made, and realizes the antibiotic and sterilizing of medical apparatus surface.
With being constantly progressive for polymer science, how by the subjects such as itself and modern medicine, biology and engineering science more
Good mutual blending becomes the problem that the present emphasis of people solves with infiltration.And in antibacterial field, photocatalysis antibacterial material application
It is not very extensive, predominantly nano TiO 2, the compatibilities of nano TiO 2 and a variety of materials, nano TiO 2 in the material steady
The service life of dispersed and storage stability, nano-TiO_2 photocatalysis anti-biotic material is determined there is also deficiency, and nano TiO 2 light is urged
Change material and applied in the production of actual industrial metaplasia simultaneously few, need further to further investigate.Comprehensively consider existing at present
For photocatalysis antibacterial class antibacterial agent there are the problem of, developing a kind of superior novel photocatalysis antibacterial agent of comprehensive performance extremely has
It is necessary.
In recent years, the characteristic of inorganic organic material surface adhesion may be implemented in the stickiness albumen of biological bivalves secretion, causes
The great attention of researcher.Small molecule dopamine (DA) containing catechol and amino has been found to can be used as imitative mussel
The presoma of adhesion protein, for developing novel mussel biomimetic material.Under weak basic condition, dopamine and its derivative meeting
It is dissolved oxygen oxidation, and spontaneous polymerization forms the PDA of the unit containing catechol of multifunction.Dopamine is due to its outstanding suction
Attached characteristic is widely used in the modification of antimicrobial surface, and achieves good results.The mild alkalinity under aerobic conditions
In environment, dopamine can almost polymerize on any surface, be formed adsorbent thin film poly-dopamine (PDA).In addition, on PDA coating
Exposed reactive group passes through the further functionalization of covalence graft polymer.PDA film can be sent out with the polymer of amino-contained
Raw schiff base reaction, so that amine-containing based polyalcohol is grafted on film by covalent bond.
Summary of the invention
The object of the present invention is to provide a kind of preparation method and applications of the photocatalysis antibacterial stain resistant material of ring-opening reaction.
Such anti-bacterial and anti-fouling agent molecule amount is controllable, and effective degree of photocatalysis monomer can be effectively controlled.This method obtains
The antibacterial antiplaque agent concentration arrived is low, and bactericidal effect is obvious, and can be used for sheet glass, polystyrene in conjunction with the characterization of adsorption of dopamine
The modification on equal surfaces, forms antibacterial surface polymer brush.Its antibacterial effect is obvious, has very high commercial potential.
Open loop method building photocatalysis antibacterial stain resistant material method, which is characterized in that polymerization reaction system include crosslinking agent,
Organic solvent, polymer monomer A and polymer monomer B；Entire polymerization reaction is carried out continuously under oxygen-free environment；Polymerization reaction body
It is each component addition sequence are as follows: polymer monomer A and polymer monomer B are first dissolved in organic solvent, crosslinking agent is then added, most
Triethylamine is added afterwards and adjusts reaction environment, makes to polymerize more preferable generation, ethylenediamine or ethanol amine is added after the reaction was completed, makes not anti-
The epoxy total overall reaction answered, polymerization obtain the polymer containing BOC group；Then the polymer containing BOC group is dissolved in two
Three not acetic acid are added in chloromethanes solution, at room temperature reaction removing BOC group, isolated photocatalysis antibacterial stain resistant material.
Polymer monomer A is the epoxide with primaquine, and polymer monomer B is N, tertbutyloxycarbonyl -1,2 second two
Amine, crosslinking agent are generally polyethyleneglycol diglycidylether, can select different molecular weight as needed.
Wherein the mass values of polymer monomer A and crosslinking agent are more excellent in 0.1-20:1 range, preferably 0.1-15:1 range
It is selected in 0.5-10:1 range；The mass values of polymer monomer B and crosslinking agent are in 0.1-25:1 range, preferably 0.1-15:1 model
It encloses, more preferable 0.5-10:1 range；The mass values of organic solvent and crosslinking agent are in 0.1-200:1 range, preferably 1-150:1 model
It encloses, more preferable 2-100:1 range
0-100 DEG C of polymeric reaction temperature, preferably 5-95 DEG C, more preferable 10-90 DEG C；The polymerization reaction time is 10-
500min, preferably 10-400min, more preferable 30-400min.
Suitable triethylamine should be added in reaction process and provide an alkaline environment for reaction, preferred polymers monomer A with
The mass ratio of triethylamine is (0.5:8)-(5:15).The quality of addition ethylenediamine or ethanol amine is 1-50 times of crosslinking agent quality,
Polymer monomer A be preferably the acid red 87 of primary amine, primary amine acid red 94 one or several kinds.
The organic solvent generally used is selected from one of sulfoxide type, amides, methylene chloride or several.
The organic solvent be selected from sulfone class, sulfoxide type, amides, alcohols one of compound or several.
Alcohol compound be generally methanol, ethyl alcohol, normal propyl alcohol, n-butanol, isopropanol, isobutanol, the tert-butyl alcohol, isoamyl alcohol,
One of n-hexyl alcohol is several.
Sulfone compound be selected from dimethyl sulfone, diethyl sulfone, dipropyl sulfone, dibutyl sulfone, diphenyl sulphone (DPS), dibenzyl sulfone, methyl phenyl sulfone,
One of sulfolane is several；The sulfoxide type is selected from dimethyl sulfoxide, diethyl sulfoxide, dipropyl sulfoxide, dibutyl
One of sulfoxide, diamylsulfoxide, dihexylsulfoxide (DHXSO) are several.
A series of corresponding polymer containing BOC group for being dissolved in water of the present invention, general processing is dissolved in water, is added
Water and the ratio of product are 100-300mL/g, are put into the bag filter of different molecular weight cut off after product dissolution to remove
The small-molecule substance not reacted, dialysis procedure continue 3 days, finally by the product freeze-drying in bag filter until removing all water
Point.
The preparation method of antimicrobial coating of the present invention: photocatalysis antibacterial material is made into the antibacterial agent water of 1-4mg/mL
Solution；Substrate is immersed in the Tris-HCl solution of the dopamine of 1-4mg/mL, overnight, the more of surface are washed with deionized water
Then bar amine is immersed in the sodium metaperiodate aqueous solution that concentration is 0.5-1mg/mL 5-10 minutes, after rinsing well, finally impregnates
- the 48h for 24 hours in antibacterial agent aqueous solution, substrate is taken out, and deionized water is rinsed, and is modified in substrate surface with being dried with nitrogen
To antimicrobial coating.The material of the substrate is selected from glass, polystyrene, plastics, ceramics, silicon.The Tris-HCl solution
PH value within the scope of 7-9, preferably pH=8.5.
In reaction system of the invention, the introducing of the amino of primaquine epoxy ring opening reaction is from effective photocatalysis antibacterial agent list
Body itself starts, and can introduce primary amino group by the way that the carboxylic group of effective photocatalysis antibacterial agent monomer itself is carried out substitution reaction
Group, and then carry out subsequent ring-opening reaction.
This kind of ring-opening reaction is usually that the specific functional groups on polymer are formed by ring-opening reaction.This Type of Collective
The usual structure of object is containing primary amino group and epoxy group, and wherein primary amino group and epoxy group can be polymer institute's band itself or pass through
Chemical reaction connects.
Beneficial outcomes: it is 7000-15000 that the present invention, which obtains molecular size range using ring-opening reaction legal system, and molecular weight distribution exists
The polymer of 1.2-1.5.For in ring opening process: (1) primaquine epoxy addition, or pass through ED, DED or in which both any mixed
A series of antibacterial agent polymer matrices that the ring-opening reaction that the open loops such as conjunction remove the complete primaquine group of unreacted obtains are complete
Standard-sized sheet ring.(2) the open loop ratio of the antibacterial agent polymer matrices obtained by mixing open loop, mixing Ring Opening Reagent can
Control.(3) in ring-opening reaction, the percentage of the effective antibacterial agent monomer of the photocatalysis of introducing is controllable.(4) all types obtained
Antibacterial antiplaque agent effect it is obvious, MIC value can be down to 32 μ g/L.(6) antimicrobial coating, antibacterial surface can be formed in conjunction with dopamine
Effect is obvious.
This method is simple and easy, and polymerization ensure that effective photochemical catalyst is controllable, and product is to Escherichia coli
(E.coil), Pseudomonas aeruginosa (P.aeruginosa), Friedlander's bacillus (K.peneumoniae), staphylococcus aureus
(S.aureus) and bacillus subtilis (B.subtilis) has an apparent fungistatic effect, part optimum allowable concentrations down to
32μg/L.In addition, using dopamine it is distinctive can be attached on that nearly all material shows stick property, by sheet glass with more
After bar amine-modified, the photocatalysis antibacterial agent with amino can by the effect of functional group on amino and poly-dopamine, glass,
The surfaces such as polystyrene form antibacterial polymer brush, to achieve the effect that surface anti-pollution.
Detailed description of the invention
The bacteriostasis rate curve graph of the EY-PEGDGE-ED of various concentration in Fig. 1 embodiment 3.
Antibacterial agent in Fig. 2 embodiment 4 photocatalysis and under the conditions of without photocatalysis to the anti-stick attached drawing of Escherichia coli.
Specific embodiment
Below with reference to embodiment, the present invention will be further described, but the present invention is not limited to following embodiments.
Example 1
1mmol acid red 87 is taken to be dissolved completely in 5mLN, in dinethylformamide (DMF), then by the 3- bromine of 1.5mmol
Propylamine hydrobromate is dissolved in the solution, is wrapped up with tinfoil.System reacts 7h under 80 DEG C of environment, and the stirring of 20mL ether is added
Then 18h is added 20mL deionized water and stirs 18h, is centrifuged with centrifuge, to remove unreacted acid red 87 and 3- bromine propylamine
Hydrobromate and most solvent DMF.It is put into the product in vacuum oven after drying for 24 hours after centrifugation as red powder
End.This powder is desired product, is denoted as EY-NH2.
Example 2
The EY-NH2 for taking the embodiment 1 of 1mmol to obtain is dissolved in the DMSO of 10mL, and the poly- second of 2mmol is added thereto
The N of Hexanediol diglycidyl ether (PEGDGE) and 1mmol, tertbutyloxycarbonyl -1,2 ethylenediamine, and 1mmol triethylamine is added, with
After bubbling mode leads to nitrogen 5min, system reacts 3h under 80 DEG C, magnetic agitation.2mLED is injected with syringe later, is made not anti-
The complete ring-opening reaction of the primary amino group answered.At this moment reaction solution is precipitated with ether and is washed twice with ether, centrifugation removal upper layer is clear
Liquid after-blow dry diethyl ether, obtains yellow mucus.It is dissolved with a small amount of pure water, later with bag filter dialysis 2 days of 3500 to remove ED, it
The liquid taken out in bag filter afterwards is lyophilized to obtain red powder product, as product required for us, is denoted as EY-PEGDGE-
ED-BOC。
The number-average molecular weight (Mn) of polymer (EY-PEGDGE-ED-BOC) is 14169, molecular weight distributing index (Mw/Mn)
It is 1.05.
Example 3
The 1mmol EY-PEGDGE-ED-BOC that embodiment 2 obtains is dissolved in 10mL dichloromethane solution, 2mL tri- is added not
Acetic acid reacts 12h at room temperature, then removes dichloromethane solution by revolving, is precipitated with ether, ultrasound, centrifugation, thus will
- BOC the protecting group of EY-PEGDGE-ED-BOC removes, and obtains water-soluble photocatalysis antibacterial stain resistant material, is denoted as EY-PEGDGE-
ED。
Example 4
The antibacterial agent that the water-soluble photocatalysis antibacterial agent EY-PEGDGE-ED that embodiment 3 is obtained is made into 1mg/mL is water-soluble
Liquid, it is spare；Sheet glass is immersed in the Tris-HCl solution (pH=8.5) of the dopamine of 2mg/mL, overnight, uses deionized water
The dopamine on surface is washed away, being then immersed in concentration is 10 minutes in the sodium metaperiodate aqueous solution of 1mg/mL, after rinsing well, most
After be separately immersed in the above antibacterial agent aqueous solution for 24 hours, take out, with being dried with nitrogen the antibacterial that the modification of different antibacterial agents can be obtained
Coating.
The obtained antibacterial agent of embodiment 3 optimum allowable concentrations of (106 bacterium/mL) in Escherichia coli are 32 μ g/mL.
Claims (8)
1. the method for open loop method building photocatalysis antibacterial stain resistant material, which is characterized in that polymerization reaction system includes crosslinking agent, has
Solvent, polymer monomer A and polymer monomer B；Entire polymerization reaction is carried out continuously under oxygen-free environment；Polymerization reaction system
Each component addition sequence are as follows: polymer monomer A and polymer monomer B are first dissolved in organic solvent, crosslinking agent is then added, finally
Triethylamine is added and adjusts reaction environment, makes to polymerize more preferable generation, ethylenediamine or ethanol amine are added after the reaction was completed, makes unreacted
Epoxy total overall reaction, polymerization obtains being dissolved in water containing the polymer of BOC group, amount of water and described above poly-
The ratio for closing the obtained polymer containing BOC group is 100-300mL/g, and what polymerization described above obtained contains BOC base
It is put into bag filter after the polymer dissolution of group to remove the small-molecule substance not reacted, dialysis procedure continues 3 days, finally will
The polymers freeze containing BOC group in bag filter is dry until removing all moisture；Then it will contain BOC in bag filter
The polymer product of group is dissolved in dichloromethane solution, and trifluoroacetic acid is added, and reaction removing BOC group, isolated at room temperature
Photocatalysis antibacterial stain resistant material；
Polymer monomer A is the acid red 87 of primary amine, and polymer monomer B is N- tertbutyloxycarbonyl -1,2 ethylenediamine, crosslinking agent
For polyethyleneglycol diglycidylether；Suitable triethylamine should be added in reaction process and provide an alkaline environment for reaction.
2. the method for open loop method building photocatalysis antibacterial stain resistant material described in accordance with the claim 1, which is characterized in that
The mass values of polymer monomer A and crosslinking agent are in 0.1-20:1 range；The mass values of polymer monomer B and crosslinking agent
In 0.1-25:1 range；The mass values of organic solvent and crosslinking agent are in 0.1-200:1 range；0-100 DEG C of polymeric reaction temperature；
The polymerization reaction time is 10-500min；
The mass ratio of polymer monomer A and triethylamine is (0.5:8)-(5:15)；The quality that ethylenediamine or ethanol amine is added is to hand over
Join 1-50 times of agent quality.
3. the method for the open loop method building photocatalysis antibacterial stain resistant material according to claim 2, which is characterized in that polymerization
The mass values of object monomer A and crosslinking agent are 0.1-15:1；The mass ratio of polymer monomer B and crosslinking agent is 0.1-25:1；Have
The mass ratio of solvent and crosslinking agent is 1-150:1；5-95 DEG C of polymeric reaction temperature, polymerization reaction time 10-400min.
4. the method for the open loop method building photocatalysis antibacterial stain resistant material according to claim 2, which is characterized in that polymerization
The mass values of object monomer A and crosslinking agent are 0.5-10:1；The mass ratio of polymer monomer B and crosslinking agent is 0.5-10:1；Have
The mass ratio of solvent and crosslinking agent is 2-100:1；10-90 DEG C of polymeric reaction temperature, polymerization reaction time 30-400min.
5. the method for the open loop method building photocatalysis antibacterial stain resistant material according to claim 1, which is characterized in that organic
Solvent be selected from sulfone class, sulfoxide type, amides, alcohols one of compound or several.
6. the method for the open loop method building photocatalysis antibacterial stain resistant material according to claim 5, which is characterized in that alcohols
Compound be one of methanol, ethyl alcohol, normal propyl alcohol, n-butanol, isopropanol, isobutanol, the tert-butyl alcohol, isoamyl alcohol, n-hexyl alcohol or
Person is several；
Sulfone compound is selected from dimethyl sulfone, diethyl sulfone, dipropyl sulfone, dibutyl sulfone, diphenyl sulphone (DPS), dibenzyl sulfone, methyl phenyl sulfone, ring fourth
One of sulfone is several；The sulfoxide type be selected from dimethyl sulfoxide, diethyl sulfoxide, dipropyl sulfoxide, dibutyl sulfoxide,
One of diamylsulfoxide, dihexylsulfoxide (DHXSO) are several.
7. the photocatalysis antibacterial stain resistant material being prepared according to any one of claim 1-6 method.
8. preparing the side of antimicrobial coating using the photocatalysis antibacterial stain resistant material that any one of claim 1-6 method is prepared
Method, which comprises the following steps: photocatalysis antibacterial material is made into the antibacterial agent aqueous solution of 1-4mg/mL；By substrate
It is immersed in the Tris-HCl solution of the dopamine of 1-4mg/mL, overnight, the dopamine on surface is washed with deionized water, then soaks
It steeps in the sodium metaperiodate aqueous solution that concentration is 0.5-1mg/mL 5-10 minutes, after rinsing well, is finally immersed in antibacterial agent water
- 48h for 24 hours in solution, substrate is taken out, and deionized water is rinsed, and modifies to obtain antimicrobial coating in substrate surface with being dried with nitrogen；
The material of the substrate is selected from glass, polystyrene, plastics, ceramics, silicon；The pH value of the Tris-HCl solution is in 7-9
In range.
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| CN105801734A (en) * | 2016-03-20 | 2016-07-27 | 北京化工大学 | Preparation method of quaternary ammonium salt polymer antibacterial agent and silver-loaded compound antibacterial agent thereof on basis of ATRP method |
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