CN108559118A - A kind of antimicrobial form carries silver-colored silastic material and preparation method thereof - Google Patents

A kind of antimicrobial form carries silver-colored silastic material and preparation method thereof Download PDF

Info

Publication number
CN108559118A
CN108559118A CN201810008478.7A CN201810008478A CN108559118A CN 108559118 A CN108559118 A CN 108559118A CN 201810008478 A CN201810008478 A CN 201810008478A CN 108559118 A CN108559118 A CN 108559118A
Authority
CN
China
Prior art keywords
silicon rubber
silver
dopamine
colored
poly
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
Application number
CN201810008478.7A
Other languages
Chinese (zh)
Inventor
吴叔青
曹琴
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
South China University of Technology SCUT
Original Assignee
South China University of Technology SCUT
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by South China University of Technology SCUT filed Critical South China University of Technology SCUT
Priority to CN201810008478.7A priority Critical patent/CN108559118A/en
Publication of CN108559118A publication Critical patent/CN108559118A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/28—Treatment by wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • C08J7/0423—Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
    • C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Materials For Medical Uses (AREA)

Abstract

The invention belongs to the technical field of biomedical material, discloses a kind of antimicrobial form and carry silver-colored silastic material and preparation method thereof.Method is：(1) ultraviolet irradiation is used, surface active is carried out to silicon rubber, obtains activation silicon rubber；(2) poly-dopamine is coated in activation silastic surface, obtains the silicon rubber of surface cladding poly-dopamine；(3) the immobilized nano silver particles of silastic surface that poly-dopamine is coated on surface obtain antimicrobial form and carry silver-colored silastic material.The method of the present invention is simple, it is easy to accomplish；Silicon rubber is enable to generate chemical bonding or hydrogen bond action with poly-dopamine simultaneously so that uniform, secured, the fine and close surface for being coated on silicon rubber of poly-dopamine；Nano silver particles are immobilized on the surface of silicon rubber by the method for reduction, and nano silver particles have very stable immobilized property；In addition, antimicrobial form prepared by the present invention, which carries silver-colored silicon rubber, has notable, lasting antibacterial action.

Description

A kind of antimicrobial form carries silver-colored silastic material and preparation method thereof
Technical field
The invention belongs to the technical fields of biomedical material, and in particular to a kind of antibacterial of surface deposition nano silver particles Type carries silver-colored silastic material and preparation method thereof.
Background technology
Silicon rubber due to good chemical stability, nontoxicity, without sensitization, good biocompatibility and good Good processing performance etc., has a wide range of applications, common medical grade silicon rubber product has catheter, lift face to repair in biologic medical field Multiple implant, medical dressing etc..But the intramolecule polarity of silicon rubber is low, results in the low-surface-energy of silicon rubber and extremely strong Surface hydrophobic, this makes bacterium be easily adhered on silastic material surface.For the patient, bacterial adhesion easily causes wound Mouthfeel contaminates, and even results in more serious consequence, it is therefore necessary to carry out surface modification to silicon rubber, improve its anti-microbial property.
The usual grain size of silver system nano-particle is smaller, between 1~100nm, has larger specific surface area, research shows that Nano silver particles have significant broad spectrum antibacterial.Nano silver particles can be adsorbed on cell membrane or enter cell interior, with egg Sulfydryl, amino groups reaction in white matter, nucleic acid, influence the normal function and proliferation activity of bacterium, to play antibacterial effect. The composite material of incorporation nano silver particles is widely used in bio-medical field, such as medical application, bandage, operation stitching Line, sterilization ointment etc..
Dopamine is a kind of neurotransmitter secreted in human brain, structure and marine mussel class bio secretion Byssus protein has similarity.Dopamine can be adhered to various by the poly-dopamine generated after selfoxidation-reduction reaction Material surface, and also contain a large amount of neck resorcinol groups in molecule monomer, these groups being capable of complexation of metal ions and effective Restore some precious metal ions, such as Au3+、Pt3+、Ag+Deng.Using this characteristic of dopamine, a variety of surfaces may be implemented and carry silver The preparation of composite material.Although the adhesive mechanism of poly-dopamine is not yet completely clear at present, researcher generally believes poly- Catechol group in dopamine molecule plays important function, and action mode is divided into chemistry according to the surface nature of matrix Key acts on and non-bonding effect.
Currently with adhesiveness of the poly-dopamine in material surface and the reproducibility to metal ion come to other matrixes into The method of row surface metalation processing it has been reported that still for surface inertness, the silicon rubber there is no active site, if It is direct cladding poly-dopamine, because power the effects that without chemical bond, hydrogen bond, clad have insecure and coating thickness Limit, if further in surface reduction nano silver, also insecure between obtained nano-silver layer and silicone rubber matrix, material is difficult to With lasting, effective antibiotic property.
Application No. is 201510174866.9 Chinese patent applications to disclose a kind of antibiotic property method of modifying of silicon rubber, Silver ion is injected into silicon rubber using ion implantation, obtained silicon rubber has antibiotic property, hydrophily and good biofacies Capacitive.But the antibiotic property silicon rubber for directly obtaining silver ion implantation silastic surface does not have lasting anti-microbial property, only It can be used as short-term anti-biotic material.
Application No. is 201510790054.7 Chinese patents to disclose a kind of antibacterial super slippery medical material and its preparation side Medical silica-gel is impregnated in antibacterial material solution, is swollen by method and antibacterial super slippery urethral catheter, obtains load antibacterial material Then silica gel coats poly-dopamine layer, obtains the lasting antibacterial super slippery medical material of antibiotic property.But by being swollen silica gel load Antibacterial material quantity it is extremely limited, antibacterial effect well cannot be reached.
Invention content
In order to overcome the shortcomings and deficiencies of the prior art, the purpose of the present invention is to provide a kind of antimicrobial forms to carry silver-colored silicon rubber Material and preparation method thereof.The silver-colored silastic material stability of antimicrobial form load provided by the invention is good and is imitated with lasting antibacterial Fruit.
The purpose of the present invention is achieved through the following technical solutions：
A kind of antimicrobial form carries the preparation method of silver-colored silastic material, includes the following steps：
(1) ultraviolet irradiation is used, surface active is carried out to silicon rubber, obtains activation silicon rubber；
(2) poly-dopamine is coated in activation silastic surface, obtains the silicon rubber of surface cladding poly-dopamine；
(3) the immobilized nano silver particles of silastic surface that poly-dopamine is coated on surface obtain antimicrobial form and carry silver-colored silicon rubber Material.
Silicon rubber described in step (1) is heat vulcanized silicone rubber or room temperature vulcanized silicone rubber.The preferred first of silicon rubber Base vinylsiloxane rubber, dimethyl silicone polymer etc..
The condition of ultraviolet irradiation described in step (1) is：10~400nm of irradiation wavelengths, preferably 100~200nm；Irradiation 1~100mW/cm of intensity2；1~2000s of irradiation time, preferably 30~300s；
The ultraviolet irradiation is preferably VUV Irradiation.
Step (1) is as follows：The silicon rubber of clean surface is placed under ultraviolet lamp, irradiation wavelengths 10~ 400nm, 1~100mW/cm of irradiation intensity2, 1~2000s of irradiation time obtains activation silicon rubber of the surface containing Si-OH.
The silicon rubber of the cladding poly-dopamine of surface described in step (2) is prepared by the following method to obtain：Silicon rubber will be activated Glue is soaked in the solution containing dopamine, is reacted under air atmosphere or oxygen atmosphere, is cleaned, drying, and it is poly- to obtain surface cladding The silicon rubber of dopamine.
The time of the reaction is 1~48h, preferably 12~36h.The cleaning refers to being cleaned with water.
A concentration of 0.1~20g/L of the dopamine solution, preferably：0.5~10g/L；The pH of the dopamine solution It is 5~12, preferably 7.5~9；
The temperature of the reaction is 5~90 DEG C, preferably room temperature.
The specific steps of the immobilized nano silver particles of silastic surface of poly-dopamine are coated described in step (3) on surface For：The silicon rubber that the surface of step (2) is coated to poly-dopamine is immersed in silver ion solution, is reacted, and is cleaned, and drying obtains The antimicrobial form that surface deposits nano silver carries silver-colored silastic material；The silver ion solution be containing free silver ion or complex silver from The solution of son.
A concentration of 0.1~30g/L of the silver ion solution；The solution of the free silver ion refers to containing Ag in solution+；The solution of the complexing silver ion refers to that silver ion exists in the form of complex state in solution, such as：Silver ammino solution；
The temperature of the reaction is 5~70 DEG C, preferably room temperature；The time of the reaction be 0.1~10h, preferably 0.5 ~3h.
The antimicrobial form carries silver-colored silastic material and is prepared by the above method.
The antimicrobial form carries silver-colored silastic material and is used as medical grade silicon rubber material.
The antimicrobial form of the present invention carries silver-colored silastic material by silicone rubber matrix and surface cladding through ultraviolet lamp activating surface Poly-dopamine layer and immobilized nano-silver layer composition.There are chemical interactions or hydrogen between silicone rubber matrix and poly-dopamine layer Key active force.
The present invention first irradiates silicon rubber under vacuum UV lamp to obtain polar Si-OH groups, then again by silicon Rubber is immersed in dopamine solution, by chemical bonding or hydrogen bond action, obtains firm poly-dopamine adsorption layer, then pass through The immobilized nano silver particles of absorbing and reducing.
Compared with prior art, the invention has the advantages that and advantageous effect：
(1) present invention carries out silicon rubber using the high-energy irradiation of ultraviolet lamp the activation process of effective essence so that after The poly-dopamine layer of continuous cladding is uniform, secured, fine and close；
(2) for the present invention using the reproducibility of poly-dopamine in the immobilized nano silver particles of silastic surface, method is simple and practicable, And the size uniform of nano silver particles, there is very stable immobilized property；
(3) antimicrobial form prepared by the present invention, which carries silver-colored silicon rubber, has notable, lasting antibacterial action.
Description of the drawings
Fig. 1 is the surface of non-activated surface coats poly-dopamine in embodiment 1 silicon rubber (SF-PDA) (a) and activation The surface SEM figures of the silicon rubber (Activated-SF-PDA) (b) of poly-dopamine are coated, the upper right corner is water contact angle figure in figure；
Fig. 2 is the surface of non-activated surface coats poly-dopamine in embodiment 2 silicon rubber (SF-PDA) (a) and activation The silicon rubber (Activated-SF-PDA) (b) for coating poly-dopamine is schemed by the surface SEM being ultrasonically treated respectively；
Fig. 3 is the scanning electron microscope (SEM) photograph that antimicrobial form prepared by embodiment 3 carries silver-colored silicon rubber；
Fig. 4 is the EDS detection elements spectrograms that antimicrobial form prepared by embodiment 3 carries silver-colored silicon rubber；
Fig. 5 is that antimicrobial form prepared by embodiment 4 carries silver-colored silicon rubber to Escherichia coli and staphylococcus aureus antibiotic property Flat-plate bacterial colony figure and antibiotic rate block diagram；A is the silicon rubber of cladding poly-dopamine after silicon rubber (unmodified silicon rubber), surface active Glue and antimicrobial form carry silver-colored silicon rubber (surface carries silver-colored silicon rubber) to the tablet bacterium of Escherichia coli and staphylococcus aureus antibiotic property Figure is fallen, b carries the anti-of silver-colored silicon rubber (surface carries silver silicon rubber) for the silicon rubber and antimicrobial form of cladding poly-dopamine after surface active Bacterium rate block diagram；
Fig. 6 is that the silver-colored silicon rubber of antimicrobial form load prepared by embodiment 5 impregnates in 0.9%NaCl solution, different soaking times Silver content change curve in lower solution.
Specific implementation mode
With reference to specific embodiments and the drawings, the present invention is described in further detail, however, the present invention is not limited thereto.
Embodiment 1
(1) by 20 × 20mm2Silicon rubber (from Guangdong Biaomei Silicon and Fluoride New Materials Co., Ltd. buy heat cure silicon rubber Glue) it is placed on Xe2 *(irradiation wavelengths 172nm, irradiation intensity 90mW/cm under quasi-molecule vacuum UV lamp2), 180s is irradiated, is obtained The silicon rubber of surface active；
(2) silicon rubber of surface active is dipped into the aqueous dopamine solution (pH of solution is 8) of concentration 2g/L, 50 DEG C Lower reaction 20h takes out, after deionized water is rinsed 3 times, nitrogen drying, and the silicon rubber of the surface cladding poly-dopamine activated, Labeled as Activated-SF-PDA；
(3) silicon rubber without surface active is dipped into the aqueous dopamine solution (pH of solution is 8) of concentration 2g/L, 20h is reacted at 50 DEG C, is taken out, and after deionized water is rinsed 3 times, nitrogen drying obtains non-activated surface cladding poly-dopamine Silicon rubber (contrast sample) is labeled as SF-PDA；
(4) silver nitrate solution of 15g/L is configured, ammonium hydroxide to solution, which is slowly added dropwise, becomes clear, obtains silver ammino solution； The SF-PDA of the Activated-SF-PDA of step (2) and step (3) are dipped into silver ammino solution respectively, after 70 DEG C of reaction 1h It takes out, deionized water is rinsed 3 times, nitrogen drying, and the antimicrobial form for respectively obtaining two kinds of immobilized nano silver particles in surface carries silver-colored silicon rubber Glue is denoted as activation-SF-PDA-Ag and unactivated-SF-PDA-Ag.
The appearance of silicon rubber (raw material) is transparent in the present embodiment, and the surfaces SF-PDA and Activated-SF-PDA have One layer of dark brown color substance, illustrates that poly-dopamine is successfully coated on silastic surface；SF-PDA and Activated-SF-PDA is compared, Visually observe it can be seen that after surface activation process when coating poly-dopamine the thicker i.e. Activated-SF-PDA of clad The clad of middle poly-dopamine is thicker than SF-PDA.
Fig. 1 is the table of non-activated surface coats poly-dopamine in the present embodiment silicon rubber (SF-PDA) (a) and activation Bread covers the surface SEM figures of the silicon rubber (Activated-SF-PDA) (b) of poly-dopamine, and the upper right corner is water contact angle in figure Figure.(a) and (b) of comparison diagram 1, it can be seen that the surfaces SF-PDA and Activated-SF-PDA are attached to poly-dopamine Grain, but there is more fold on the surfaces SF-PDA, and the surfaces Activated-SF-PDA do not have fold, poly-dopamine particle uniform Distribution；WCA (water contact angle) is respectively 64.3 ° and 45.8 °, and SF-PDA and Activated-SF-PDA show hydrophily, But Activated-SF-PDA hydrophilies are significantly better than SF-PDA.This demonstrate that being conducive in silicon rubber through surface activation process Surface forms thicker poly-dopamine layer.
Embodiment 2
(1) by 20 × 20mm2Silicon rubber (from Guangdong Charming Co., Ltd. buy heat vulcanized silicone rubber) place (irradiation wavelengths 167.7nm, irradiation intensity 70mW/cm under vacuum UV lamp2), 60s is irradiated, the silicon rubber of surface active is obtained Glue；
(2) silicon rubber of surface active is dipped into the aqueous dopamine solution (pH 7) of concentration 20g/L, in oxygen atmosphere It after enclosing lower room temperature reaction 48h, takes out, after deionized water is rinsed 3 times, nitrogen drying obtains activating surface cladding poly-dopamine Silicon rubber is labeled as Activated-SF-PDA；
(3) silicon rubber without surface activation process is directly dipped into the aqueous dopamine solution (pH 7) of concentration 20g/L In, it after reacting at room temperature 48h under oxygen atmosphere, takes out, after deionized water is rinsed 3 times, nitrogen drying obtains non-activated surface The silicon rubber (contrast sample) of poly-dopamine is coated, SF-PDA is labeled as；
(5) silver nitrate solution of 30g/L is configured, ammonium hydroxide to solution, which is slowly added dropwise, becomes clear, obtains silver ammino solution； The SF-PDA of the Activated-SF-PDA of step (2) and step (3) are dipped into silver ammino solution respectively, 5 DEG C of reaction 0.1h After take out, deionized water is rinsed 3 times, and nitrogen drying, the antimicrobial form for obtaining the immobilized nano silver particles in surface carries silver-colored silicon rubber.
The SF-PDA of the Activated-SF-PDA of step (2) and step (3) are respectively put into the appearance equipped with deionized water In device, the sonic oscillation instrument for being 40kHz with frequency vibrates 30 minutes, takes out drying, and SEM figures are as shown in Figure 2.Fig. 2 is this reality Apply the silicon of the silicon rubber (SF-PDA) (a) of non-activated surface cladding poly-dopamine and the surface cladding poly-dopamine of activation in example Rubber (Activated-SF-PDA) (b) is schemed by the surface SEM being ultrasonically treated respectively.As can be seen from the figure the surfaces SF-PDA There is crackle, is studded with some poly-dopamine particles, and the poly-dopamine particle on the surfaces Activated-SF-PDA is uniformly and fine and close. This result illustrates the poly-dopamine layer on Activated-SF-PDA because having chemical interactions or hydrogen bond action, in sonic oscillation Under the action of still can closely be coated on silastic surface.
Embodiment 3
(1) by 20 × 20mm2Silicon rubber (184 room temperature vulcanized silicone rubbers of DOW CORNING sylgard) be placed on vacuum ultraviolet (irradiation wavelengths 124nm, irradiation intensity are specially 30mW/cm under lamp2), 10s is irradiated, the silicon rubber of surface active is obtained；
(2) silicon rubber of surface active is dipped into the dopamine solution (pH of solution is 12) of concentration 15g/L, 5 DEG C, under oxygen atmosphere after reaction 1h, take out, after deionized water is rinsed 3 times, nitrogen drying obtains surface cladding poly-dopamine Silicon rubber；
(3) silver nitrate solution of 15g/L is configured, ammonium hydroxide to solution, which is slowly added dropwise, becomes clear, obtains silver ammino solution； The silicon rubber that the surface of step (2) is coated to poly-dopamine is dipped into silver ammino solution, is taken out after 5 DEG C of reaction 1h, deionized water It rinses 3 times, nitrogen drying, the antimicrobial form for obtaining the immobilized nano silver particles in surface carries silver-colored silicon rubber.It is tested through plate count It measures, it is 96% to the bacteriostasis rate of Pseudomonas aeruginosa that the present embodiment antimicrobial form, which carries silver-colored silicon rubber,.
Fig. 3 is the scanning electron microscope (SEM) photograph that antimicrobial form manufactured in the present embodiment carries silver-colored silicon rubber.As can be seen from Figure 3 silicon rubber One layer of fine and close nano-Ag particles are accumulated in surface.
Fig. 4 is the EDS detection elements spectrograms that antimicrobial form manufactured in the present embodiment carries silver-colored silicon rubber.As can be known from Fig. 4, this is anti- It is 25.60wt% that bacterial type, which carries silver-colored silastic surface silver dollar cellulose content,.
Embodiment 4
(1) by 20 × 20mm2Silicon rubber (184 room temperature vulcanized silicone rubbers of DOW CORNING sylgard) be placed on vacuum ultraviolet (irradiation wavelengths 153nm, irradiation intensity are specially 100mW/cm under lamp2), 300s is irradiated, the silicon rubber of surface active is obtained；
(2) silicon rubber of surface active is dipped into the dopamine solution (pH value of solution 9) of concentration 0.1g/L, 90 DEG C, under air atmosphere after reaction 36h, take out, after deionized water is rinsed 3 times, nitrogen drying obtains surface cladding poly-dopamine Silicon rubber；
(3) silver nitrate solution of 25g/L is configured, ammonium hydroxide to solution, which is slowly added dropwise, becomes clear；Obtained by step (2) Surface cladding poly-dopamine silicon rubber be dipped into above-mentioned silver ion solution, react 0.5h after take out, deionized water rinse 3 Secondary, nitrogen drying, the antimicrobial form for obtaining the immobilized nano silver particles in surface carries silver-colored silicon rubber.
Anti-microbial property test：
The silicon rubber of silicon rubber in the present embodiment, the cladding poly-dopamine of step (2) (is coated into poly- DOPA after surface active The silicon rubber of amine) and step (3) antimicrobial form carry silver-colored silicon rubber respectively with containing 1.0 × 106CFU Escherichia coli and golden yellow grape After coccus bacterial suspension co-cultures 6h, print is put into the test tube of the PBS containing 5ml respectively with sterile tweezer, mix well and elute Bacterium is added PBS buffer solution and is diluted to 100 times, draws 0.5ml respectively, be placed in two plates, with cool to 40~45 DEG C of 15ml's LB solid mediums (0.5% triphenyltetrazolium chloride of addition, can viable bacteria be dyed red) pour into, and rotate plate, it is made to fill Divide uniformly, tablet is overturn after agar solidification, 35 DEG C of culture 48h do the counting of viable bacteria bacterium colony.
Experiment is repeated 3 times, and is pressed examination and is calculated antibiotic rate：X=[(A-B)/A] * 100%
In formula：X --- antibiotic rate, %；
A --- control sample average colony number；
B --- subject sample average clump count.
Fig. 5 is that antimicrobial form manufactured in the present embodiment carries silver-colored silicon rubber to Escherichia coli and staphylococcus aureus antibiotic property Flat-plate bacterial colony figure and antibiotic rate block diagram, a are the silicon rubber of cladding poly-dopamine after silicon rubber (unmodified silicon rubber), surface active Glue and antimicrobial form carry silver-colored silicon rubber (surface carries silver-colored silicon rubber) to the tablet bacterium of Escherichia coli and staphylococcus aureus antibiotic property Figure is fallen, b carries the anti-of silver-colored silicon rubber (surface carries silver silicon rubber) for the silicon rubber and antimicrobial form of cladding poly-dopamine after surface active Bacterium rate block diagram.Test result shows after co-culturing 6h with Escherichia coli and staphylococcus aureus, is coated after surface active The bacterium to survive on the silicon rubber of poly-dopamine is bright compared with the bacterium to survive on silicon rubber print (silicon rubber, unmodified silicon rubber) Aobvious to reduce, antibiotic rate is respectively 68.5% and 78.4%, this is because the silicon rubber of cladding poly-dopamine does not change after the activation of face Property silicon rubber have preferable hydrophily, adherency of the bacterium in sample surfaces can be reduced, to play certain antibacterial action；It is anti- Bacterial type carries and there's almost no bacterium living on silver-colored silicon rubber, and antibiotic rate respectively reaches 100% (Escherichia coli) and 98.6% (golden yellow Staphylococcus), this is because nano silver has broad spectrum antibacterial, stronger antibiotic property is all had to various bacteria.
Embodiment 5
(1) by 20 × 20mm2Silicon rubber (Guangdong Biaomei Silicon and Fluoride New Materials Co., Ltd. production room temperature vulcanization silicon rubber Glue) it is placed under vacuum UV lamp that (irradiation wavelengths 193nm, irradiation intensity are specially 80mW/cm2), irradiation 380s, obtain surface The silicon rubber of activation；
(2) silicon rubber of surface active is dipped into the dopamine solution (pH value of solution 8.5) of concentration 8g/L, 35 DEG C, react for 24 hours under air atmosphere after, take out, after deionized water is rinsed 3 times, nitrogen drying obtains surface cladding poly-dopamine Silicon rubber；
(3) silver nitrate solution of 10g/L is configured, ammonium hydroxide to solution, which is slowly added dropwise, becomes clear, obtained by step (2) Surface cladding poly-dopamine silicon rubber be dipped into above-mentioned silver ion solution, 25 DEG C reaction 0.3h after take out, deionized water It rinses 3 times, nitrogen drying, the antimicrobial form for obtaining the immobilized nano silver particles in surface carries silver-colored silicon rubber.It is tested through plate count It measures, it is 98% to the bacteriostasis rate of staphylococcus aureus that antimicrobial form, which carries silver-colored silicon rubber,.
Durable antibiotic is tested：Antimicrobial form manufactured in the present embodiment is carried into the disk that silver-colored silicon rubber is cut into a diameter of 1mm, It is dipped into 0.9%NaCl solution, is kept in dark place at room temperature, take out sample after 3 days, 5 days, 7 days, 10 days, 15 days respectively, then 1ml 10%HNO are added into solution3The content of Ag in solution is tested in fully acidification.As a result, it has been found that as the time increases, solution The content of middle silver element is also continuously increased, and illustrates that nano-Ag particles are sustained release into solution, which carries silver-colored silicon rubber tool There is lasting biocidal property.
Fig. 6 is that the silver-colored silicon rubber of antimicrobial form manufactured in the present embodiment load impregnates in 0.9%NaCl solution, different soaking times Silver content change curve in lower solution.
Above example is the preferable embodiment of the present invention, but embodiments of the present invention are not limited by examples detailed above, It is other it is any for away from spirit of the invention and the change made under principle, modification, replacement, combine, simplification is equivalent.

Claims (8)

1. a kind of antimicrobial form carries the preparation method of silver-colored silastic material, it is characterised in that：Include the following steps：
(1) ultraviolet irradiation is used, surface active is carried out to silicon rubber, obtains activation silicon rubber；
(2) poly-dopamine is coated in activation silastic surface, obtains the silicon rubber of surface cladding poly-dopamine；
(3) the immobilized nano silver particles of silastic surface that poly-dopamine is coated on surface obtain antimicrobial form and carry silver-colored silastic material.
2. antimicrobial form carries the preparation method of silver-colored silastic material according to claim 1, it is characterised in that：Institute in step (1) The condition for stating ultraviolet irradiation is：10~400nm of irradiation wavelengths；1~100mW/cm of irradiation intensity2；1~2000s of irradiation time.
3. antimicrobial form carries the preparation method of silver-colored silastic material according to claim 2, it is characterised in that：Institute in step (1) The condition for stating ultraviolet irradiation is：100~200nm of irradiation wavelengths；1~100mW/cm of irradiation intensity2；30~300s of irradiation time.
4. antimicrobial form carries the preparation method of silver-colored silastic material according to claim 1, it is characterised in that：Institute in step (2) The silicon rubber for stating surface cladding poly-dopamine is prepared by the following method to obtain：Activation silicon rubber is soaked in containing the molten of dopamine It in liquid, reacts, cleans under air atmosphere or oxygen atmosphere, drying obtains the silicon rubber of surface cladding poly-dopamine；It is described more A concentration of 0.1~20g/L of bar amine aqueous solution；The pH of the dopamine solution is 5~12.
5. antimicrobial form carries the preparation method of silver-colored silastic material according to claim 4, it is characterised in that：The reaction when Between be 1~48h；The dopamine solution it is a concentration of：0.5~10g/L；The pH of the dopamine solution is 7.5~9；It is described The temperature of reaction is 5~90 DEG C.
6. antimicrobial form carries the preparation method of silver-colored silastic material according to claim 1, it is characterised in that：Institute in step (3) State surface coat poly-dopamine the immobilized nano silver particles of silastic surface the specific steps are：The surface of step (2) is wrapped The silicon rubber for covering poly-dopamine is immersed in silver ion solution, is reacted, and is cleaned, drying, obtains the antibacterial of surface deposition nano silver Type carries silver-colored silastic material；The silver ion solution is the solution containing free silver ion or complexing silver ion.
7. antimicrobial form carries the preparation method of silver-colored silastic material according to claim 6, it is characterised in that：The silver ion is molten A concentration of 0.1~30g/L of liquid；The solution of the free silver ion refers to containing Ag in solution+；It is described that the molten of silver ion is complexed Liquid refers to that silver ion exists in the form of complex state in solution；
The temperature of the reaction is 5~70 DEG C；The time of the reaction is 0.1~10h.
8. a kind of antimicrobial form obtained by any one of claim 1~7 preparation method carries silver-colored silastic material.
CN201810008478.7A 2018-01-04 2018-01-04 A kind of antimicrobial form carries silver-colored silastic material and preparation method thereof Pending CN108559118A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810008478.7A CN108559118A (en) 2018-01-04 2018-01-04 A kind of antimicrobial form carries silver-colored silastic material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810008478.7A CN108559118A (en) 2018-01-04 2018-01-04 A kind of antimicrobial form carries silver-colored silastic material and preparation method thereof

Publications (1)

Publication Number Publication Date
CN108559118A true CN108559118A (en) 2018-09-21

Family

ID=63529723

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810008478.7A Pending CN108559118A (en) 2018-01-04 2018-01-04 A kind of antimicrobial form carries silver-colored silastic material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN108559118A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115137669A (en) * 2022-06-24 2022-10-04 金三江(肇庆)硅材料股份有限公司 Preparation method of silicon dioxide loaded nano-silver composite material

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110091669A1 (en) * 2009-10-20 2011-04-21 The Hong Kong Polytechnic University Method for fabrication of silicone composite with antimicrobial coating
CN106178112A (en) * 2016-07-25 2016-12-07 太原理工大学 A kind of graphene oxide/polymer composite antibacterial material and preparation method thereof
CN106977757A (en) * 2017-04-27 2017-07-25 西南大学 Preparation method of dopamine silk gum laminated film of Nano Silver functionalization and products thereof and application

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110091669A1 (en) * 2009-10-20 2011-04-21 The Hong Kong Polytechnic University Method for fabrication of silicone composite with antimicrobial coating
CN106178112A (en) * 2016-07-25 2016-12-07 太原理工大学 A kind of graphene oxide/polymer composite antibacterial material and preparation method thereof
CN106977757A (en) * 2017-04-27 2017-07-25 西南大学 Preparation method of dopamine silk gum laminated film of Nano Silver functionalization and products thereof and application

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115137669A (en) * 2022-06-24 2022-10-04 金三江(肇庆)硅材料股份有限公司 Preparation method of silicon dioxide loaded nano-silver composite material

Similar Documents

Publication Publication Date Title
Guo et al. Polymer/nanosilver composite coatings for antibacterial applications
CN107096068A (en) A kind of preparation method of dentistry implant and its bioactivity antimicrobial surface
CN101708341B (en) Method for preparing Ag-carrying bacterial cellulose hydrogel antimicrobial dressing and product thereof
CN106924810B (en) A kind of nanometer antibacterium coating material and preparation method thereof based on nano-Ag particles
CN110644239B (en) Antibacterial polylactic acid nanofiber and preparation method and application thereof
CA2270258C (en) Contact-killing non-leaching antimicrobial materials
CN106178112A (en) A kind of graphene oxide/polymer composite antibacterial material and preparation method thereof
CN103768700B (en) Antibacterial catheter of albumen and preparation method thereof
CN1925819A (en) Dressing for a wound
Liu et al. Template-assisted magnetron sputtering of cotton nonwovens for wound healing application
Baek et al. In situ assembly of antifouling/bacterial silver nanoparticle-hydrogel composites with controlled particle release and matrix softening
CN101010003A (en) Antimicrobial silver compositions
CN102671239A (en) Method for preparing broad-spectrum antibacterial effect chitosan nano composite gel coating
CN102317537A (en) The living polymer film
CN110064075B (en) Self-assembled antibacterial coating based on nano silver/D-cysteine and preparation method thereof
CN104674215A (en) Preparation method of nano silver particle loaded antimicrobial titanium dioxide coating
CN106756898A (en) The preparation method of antibacterial hydrophobic ZnO nanorod
CN102357265A (en) Surface modification polyurethane central venous catheter and preparation method thereof
CN105999407A (en) Method for preparing broad-spectrum long-acting antibacterial anti-adhesive chitosan nano silver composite gel coating layer
CN108559118A (en) A kind of antimicrobial form carries silver-colored silastic material and preparation method thereof
RU2416435C1 (en) Method of antiseptic surface preparation of product made of polymeric material
CN110408189A (en) A method of improving medical polyurethane material blood compatibility and antibiotic property
CN100535182C (en) Method for preparing silver nano antibacterial material
CN104353109B (en) Method for modifying titanium with antibacterial property and effect of promoting growth of osteoblasts
Teterycz et al. Deposition of zinc oxide on the materials used in medicine. Preliminary results

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: 20180921

RJ01 Rejection of invention patent application after publication