CN104141133B - A kind of preparation method of anti-bacteria stainless steel material of Ionic Liquid Modified - Google Patents
A kind of preparation method of anti-bacteria stainless steel material of Ionic Liquid Modified Download PDFInfo
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- CN104141133B CN104141133B CN201410373147.5A CN201410373147A CN104141133B CN 104141133 B CN104141133 B CN 104141133B CN 201410373147 A CN201410373147 A CN 201410373147A CN 104141133 B CN104141133 B CN 104141133B
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Abstract
A preparation method for the anti-bacteria stainless steel material of Ionic Liquid Modified, relates to the preparation of stainless material.Stainless steel surface is carried out pre-treatment, drop into put into after carrying out stainless steel surface hydroxylation in the mixing solutions of hydrogen peroxide and sulfuric acid γ the solution of mercaptopropyl trimethoxysilane, with methyl alcohol, ethanol or Virahol for solvent, realize stainless steel surface γ mercaptopropyl trimethoxysilane self-assembly; The stainless steel substrates obtained is put into the HCl aqueous solution; make absorption γ mercaptopropyl trimethoxysilane hydrolysis; then clean; remove HCl; gas dries up; container is put into again after solidification; add ionic liquid monomer 1 Xi Ji 3 alkyl imidazole salt, initiator and solvent carry out click-reaction; react in oil bath under inert atmosphere protection; again reaction solution is cooled, go out polymkeric substance with dehydrated alcohol sedimentation, stainless steel substrates washes of absolute alcohol; after gas dries up, namely obtain the anti-bacteria stainless steel material of Ionic Liquid Modified.
Description
Technical field
The present invention relates to the preparation of stainless material, especially relate to a kind of preparation method of anti-bacteria stainless steel material of Ionic Liquid Modified.
Background technology
Stainless steel has a wide range of applications in food engineering, boats and ships, medical treatment etc., and the research of anti-bacteria stainless steel is the problem that scientific circles pay close attention to always.From marine ship to medical device, prevent microorganism etc. from being have basic and problem that is ubiquity in the attachment of material surface and growth.The mankind can not change the adhesion characteristics of occurring in nature microorganism, and thus design has the effective way that the surface of antibacterial is the negative effect reducing and eliminate bioadhesion.
The anti-bacteria stainless steel in the past reported mostly adopts in common stainless steel and adds a certain amount of antibacterial metal silver, copper, as Japanese Patent 8 ?84822, Japanese Patent 8 ?89041, Chinese patent CN1272889A, Chinese patent CN1310246A, Chinese patent CN1310245A etc., by controlled working process, make antibacterial metal in stainless steel base with certain size, form, evenly separate out, when contacting with bacterium, by the glycation damage cytolemma with cell, destroy the normal composition of bacterial cell and the balance of procreation, thus reach antibacterial object.On the other hand, this kind of stainless material risk be discharged in environment in the process used also result in the attention of investigator.In addition, top coat anti-bacteria stainless steel also has report, but these coatings easily come off in the process used, and cause long-term antibacterial effect not to be very desirable.
Summary of the invention
Technical problem to be solved by this invention is the defect overcoming prior art, provides a kind of preparation method of anti-bacteria stainless steel material of Ionic Liquid Modified.
The present invention includes following steps:
1) stainless steel surface is carried out pre-treatment, obtain pretreated stainless steel;
2) pretreated stainless steel substrates is dropped in the mixing solutions of hydrogen peroxide and sulfuric acid, carry out stainless steel surface hydroxylation;
3) stainless steel substrates after surface hydroxylation is put into the solution of γ-mercaptopropyl trimethoxysilane (MTPS), with methyl alcohol, ethanol or Virahol for solvent, realize stainless steel surface γ-mercaptopropyl trimethoxysilane self-assembly;
4) stainless steel substrates that step 3 obtains is put into the HCl aqueous solution; make the γ-mercaptopropyl trimethoxysilane hydrolysis of absorption; then clean; remove HCl; gas dries up; container is put into again after solidification; add ionic liquid monomer 1-thiazolinyl-3-alkyl imidazole salt, initiator and solvent and carry out click-reaction; react in oil bath under inert atmosphere protection; again reaction solution is cooled, go out polymkeric substance with dehydrated alcohol sedimentation, stainless steel substrates washes of absolute alcohol; after gas dries up, namely obtain the anti-bacteria stainless steel material of Ionic Liquid Modified.
In step 1) in, described pretreated method can be: carry out polishing with sand paper, 0.5% ~ 1.0% (mass percent) NaOH aqueous solution alkali cleaning, 5 ~ 10min, with water cleaning, to dry up with acetone cleaning, gas successively.
In step 2) in, described hydrogen peroxide can adopt mass percentage concentration be 30% hydrogen peroxide, described sulfuric acid can adopt the commercially available vitriol oil, and the volume ratio of hydrogen peroxide and sulfuric acid can be (3 ~ 7): 1; The described hydroxylated time can be 20 ~ 60min.
In step 3) in, described γ-mercaptopropyl trimethoxysilane can adopt volumetric molar concentration to be the γ-mercaptopropyl trimethoxysilane of 20 ~ 80mM; The time of described stainless steel surface γ-mercaptopropyl trimethoxysilane self-assembly can be 6 ~ 12h.
In step 4) in, the described HCl aqueous solution can adopt volumetric molar concentration to be the HCl aqueous solution of 0.1 ~ 0.05M; The time of described hydrolysis can be 6 ~ 12h; Described cleaning can use ethanol and washed with de-ionized water successively; The condition of described solidification can be 100 ~ 105 DEG C of solidification 3 ~ 8h; In described ionic liquid monomer 1-thiazolinyl-3-alkyl imidazole salt, 3-long alkyl chains is C4 ~ C18,1-alkenylalkyl carbon chain lengths is C1 ~ C12, and negatively charged ion is Br
-, BF
4 -, PF
6 -; Described initiator can adopt Diisopropyl azodicarboxylate AIBN, and the consumption of initiator can be 0.1% ~ 1% of ionic liquid monomer 1-thiazolinyl-3-alkyl imidazole salt by mass percentage; Described solvent can be selected from the one in trichloromethane, dimethyl formamide, dimethyl sulfoxide (DMSO), methyl alcohol, ethanol etc.; In described oil bath, reaction conditions can at 50 ~ 70 DEG C of reaction 6 ~ 15h; 3 times capable of washing of described cleaning.
The present invention builds the antibiotic layer with safety, durable antibiotic by adopting the method for chemical bonding at stainless steel surface, anti-bacteria stainless steel preparation method provided by the invention is simple, reaction conditions is gentle, prepared surface of stainless steel has excellent anti-microbial property, can be widely used in each industrial circle.
Accompanying drawing explanation
Fig. 1 is that unmodified stainless steel body surface atomic force microscope used in the present invention characterizes.
The stainless steel surface atomic force microscope of Fig. 2 γ constructed by the present invention-mercaptopropyl trimethoxysilane silanization characterizes.
The bromination of Fig. 3 constructed by the present invention 1 ?Yi Xi Ji ?3 ?octylimidazole Ionic Liquid Modified stainless steel surface atomic force microscope characterize.
The stainless steel antibacterial effect live bacterial count figure of Fig. 4 constructed by the present invention.
Fig. 5 is the bacterial colony scanning electron microscopic picture that its surface adhesion of 12h placed by the stainless steel of unmodified used in the present invention in E. coli broth.
The bacterial colony scanning electron microscopic picture of its surface adhesion of 12h placed by the stainless steel of the MTPS silanization of Fig. 6 constructed by the present invention in E. coli broth.
The bromination of Fig. 7 constructed by the present invention 1 ?Yi Xi Ji ?3 ?octylimidazole Ionic Liquid Modified stainless steel in E. coli broth, place the bacterial colony scanning electron microscopic picture of its surface adhesion of 12h.
Embodiment
Following examples will describe more comprehensively to the present invention.
Embodiment 1
By stainless steel substrates successively with 360#, 600# and 1000#, 1500# silicon carbide paper polishing extremely light.The stainless steel of new mill uses the 0.5%NaOH aqueous solution, deionized water, ethanol, acetone successively, each ultrasonic 5min of deionized water, and the oil stain on removing surface and impurity, nitrogen dries up, and obtains pretreated stainless steel substrates, and AFM records its surface topography as shown in Figure 1.This stainless steel substrates is dropped into the 30%H of new preparation
2o
2with the mixing solutions of the vitriol oil, 3: 1 (volume ratios), place 20min.Clean three times with water, acetone successively after taking-up, nitrogen dries up, and the stainless steel substrates after process is put into 20ml20MmMTPS ethanolic soln, after room temperature leaves standstill 6h, this stainless steel substrates is put into the 0.1MHCl aqueous solution standing 12h and the MTPS of absorption is hydrolyzed.Then thoroughly clean with ethanol and deionized water successively, after removal HCl, Ar dry up, 105 DEG C of solidification 2h, obtain the stainless steel surface of silanization, AFM records its surface topography as shown in Figure 2.The stainless steel substrates of silanization is put into 50ml container, add ionic liquid monomer bromination 1 ?Yi Xi Ji ?3 ?octylimidazole VOIm
+br
?(1.0g), AIBN (0.005g), 30ml trichloromethane, vacuumizes, inflated with nitrogen, 3 times repeatedly, at oil bath 70 DEG C, react 12h.Take out reaction solution to cool rapidly, go out polymkeric substance with dehydrated alcohol sedimentation, stainless steel substrates washes of absolute alcohol 3 times, nitrogen dries up, be labeled as SS ?SCA ?VOIm
+br
?.AFM records its surface topography as shown in Figure 3.
After Figure 4 shows that the stainless steel surface of unmodified, silanization stainless steel surface and Ionic Liquid Modified, the bacteria in viable cell counting of 12h rear surface placed by stainless steel in intestinal bacteria solution, and 12h surface E. coli clones surface sweeping electron microscopic picture placed by the stainless steel that Fig. 5 ~ Fig. 7 is respectively blank stainless steel, silanization stainless steel and Ionic Liquid Modified in E. coli broth.As can be seen from the figure, with blank stainless steel, the stainless steel surface of silanization is compared, and faced by the Stainless Steel Watch of Ionic Liquid Modified, intestinal bacteria have obvious inhibition.
Embodiment 2
By stainless steel substrates successively with 360#, 600# and 1000#, 1500# silicon carbide paper polishing extremely light.The stainless steel of new mill uses 0.7%NaOH successively, deionized water, ethanol, acetone, and deionized water is each ultrasonic 10min at room temperature, and the oil stain on removing surface and impurity, nitrogen dries up.Pretreated stainless steel substrates is dropped into the 30%H of new preparation
2o
2with vitriol oil mixing solutions, 4: 1 (volume ratios), room temperature 30min.Take out and clean three times with water, acetone successively, nitrogen dries up, and the stainless steel substrates after process is put into 20ml30mMMTPS methanol solution, after room temperature leaves standstill 6h, this stainless steel substrates is put into the 0.05MHCl aqueous solution and leave standstill the silane hydrolyzate that 6h makes absorption.Then thoroughly clean with ethanol and deionized water successively, remove HCl, Ar and dry up, 105 DEG C of solidification 2h, obtain silanization stainless steel surface.The stainless steel substrates of silanization is put into 50ml container, add ionic liquid monomer bromination 1 ?Yi Xi Ji ?3 ?butyl imidazole tetrafluoro boron salt VbIm
+bF
4 ?(1.0g), AIBN (0.001g), 30ml methyl alcohol, vacuumizes, inflated with nitrogen, 3 times repeatedly, 70 DEG C of reaction 12h in oil bath.Take out reaction solution to cool rapidly, go out polymkeric substance with dehydrated alcohol sedimentation, stainless steel substrates washes of absolute alcohol 3 times, nitrogen dries up, and obtains ionic liquid VbIm
+bF
4 ?the stainless steel surface modified.
Embodiment 3
By stainless steel substrates successively with 360#, 600# and 1000#, 1500# silicon carbide paper polishing extremely light.The stainless steel of new mill uses 0.9%NaOH successively, deionized water, ethanol, acetone, and deionized water is each ultrasonic 6min at room temperature, and the oil stain on removing surface and impurity, nitrogen dries up.Pretreated stainless steel substrates is dropped into the 30%H of new preparation
2o
2with vitriol oil mixing solutions, 5: 1 (volume ratios), place 40min.Clean three times with water, acetone successively after taking-up, nitrogen dries up, and the stainless steel substrates after process is put into 20ml40mMMTPS ethanolic soln, and room temperature places 6h.Subsequently this stainless steel substrates is put into the 0.05MHCl aqueous solution to leave standstill 8h the MTPS of absorption is hydrolyzed.Then thoroughly clean with ethanol and deionized water successively, remove HCl, Ar and dry up, 70 DEG C of solidification 4h, obtain silanization stainless steel surface.The stainless steel substrates of silanization is put into 50ml container, add ionic liquid monomer 1 ?Bing Xi Ji ?3 ?amyl group imidazoles hexafluoro microcosmic salt PpIm
+pF
6 ?(0.8g), AIBN (0.004g), 20ml ethanol, vacuumizes, inflated with nitrogen, three times repeatedly, 60 DEG C of reaction 12h in oil bath.Take out reaction solution to cool rapidly, go out polymkeric substance with dehydrated alcohol sedimentation, stainless steel substrates washes of absolute alcohol three times, nitrogen dries up, and obtains ionic liquid PpIm
+pF
6 ?the stainless steel surface modified.
Embodiment 4
By stainless steel substrates successively with 360#, 600# and 1000#, 1500# silicon carbide paper polishing extremely light.The stainless steel of new mill uses 1.0%NaOH successively, deionized water, ethanol, acetone, each ultrasonic 10min of deionized water, and the oil stain on removing surface and impurity, nitrogen dries up.Pretreated stainless steel substrates is dropped into the vitriol oil and the 30%H of new preparation
2o
2mixing solutions, 7: 1 (volume ratios), room temperature places 60min.Take out and clean three times with water, acetone successively, nitrogen dries up.Stainless steel substrates after process is put into 20ml60mMMTPS aqueous isopropanol, and room temperature leaves standstill 6h.This stainless steel substrates being put into the standing 10h of the 0.1MHCl aqueous solution makes the MTPS of absorption be hydrolyzed again.Then thoroughly clean with ethanol and deionized water successively, remove HCl, Ar and dry up, 80 DEG C of solidification 3h, obtain silanization stainless steel surface.The stainless steel substrates of silanization is put into 50ml container, add ionic liquid monomer 1 ?Ding Xi Ji ?3 ?butyl imidazole hexafluoro microcosmic salt BbIm
+pF
6 ?(0.5g), AIBN (0.003g), 30ml dimethyl formamide, vacuumizes, inflated with nitrogen, three times repeatedly, 60 DEG C of reaction 8h in oil bath.Take out reaction solution to cool rapidly, go out polymkeric substance with dehydrated alcohol sedimentation, stainless steel substrates washes of absolute alcohol three times, nitrogen dries up, and obtains ionic liquid BbIm
+pF
6 ?the stainless steel surface modified.
Embodiment 5
By stainless steel substrates successively with 360#, 600# and 1000#, 1500# silicon carbide paper polishing extremely light.The stainless steel of new mill uses 0.5%NaOH successively, deionized water, ethanol, acetone, and deionized water is each ultrasonic 5min at room temperature, and the oil stain on removing surface and impurity, nitrogen dries up.Pretreated stainless steel substrates is dropped into the vitriol oil and the 30%H of new preparation
2o
2mixing solutions, 7: 1 (volume ratios), room temperature places 60min.Clean three times with water, acetone successively after taking-up, nitrogen dries up, and the stainless steel substrates after process is put into 20ml80mMMTPS methanol solution, and room temperature leaves standstill 12h.Subsequently this stainless steel substrates being put into the standing 6h of the 0.1MHCl aqueous solution makes the MTPS of absorption be hydrolyzed.Then thoroughly clean with ethanol and deionized water successively, remove HCl, Ar and dry up, 100 DEG C of fixing 2h, obtain silanization stainless steel surface.The stainless steel substrates of silanization is put into 50ml container, add ionic liquid monomer 1 ?Ding Xi Ji ?3 ?heptyl imidazoles hexafluoro microcosmic salt BhIm
+pF
6 ?(0.5g), AIBN (0.004g), 40ml dimethyl sulfoxide (DMSO), vacuumizes, applying argon gas, three times repeatedly, 60 DEG C of reaction 10h in oil bath.Take out reaction solution to cool rapidly, go out polymkeric substance with dehydrated alcohol sedimentation, stainless steel substrates washes of absolute alcohol three times, nitrogen dries up, and obtains ionic liquid BhIm
+pF
6 ?the stainless steel surface modified.
Claims (10)
1. a preparation method for the anti-bacteria stainless steel material of Ionic Liquid Modified, is characterized in that comprising the steps:
1) stainless steel surface is carried out pre-treatment, obtain pretreated stainless steel;
2) pretreated stainless steel substrates is dropped in the mixing solutions of hydrogen peroxide and sulfuric acid, carry out stainless steel surface hydroxylation;
3) stainless steel substrates after surface hydroxylation is put into the solution of γ-mercaptopropyl trimethoxysilane (MTPS), with methyl alcohol, ethanol or Virahol for solvent, realize stainless steel surface γ-mercaptopropyl trimethoxysilane self-assembly;
4) by step 3) stainless steel substrates that obtains puts into the HCl aqueous solution; make the γ-mercaptopropyl trimethoxysilane hydrolysis of absorption; then clean; remove HCl; gas dries up; container is put into again after solidification; add ionic liquid monomer 1-thiazolinyl-3-alkyl imidazole salt, initiator and solvent and carry out click-reaction; react in oil bath under inert atmosphere protection; again reaction solution is cooled, go out polymkeric substance with dehydrated alcohol sedimentation, stainless steel substrates washes of absolute alcohol; after gas dries up, namely obtain the anti-bacteria stainless steel material of Ionic Liquid Modified.
2. the preparation method of a kind of anti-bacteria stainless steel material of Ionic Liquid Modified as claimed in claim 1, it is characterized in that in step 1) in, described pretreated method is: successively with sand paper carry out polishing, mass percentage concentration is 0.5% ~ 1.0%NaOH aqueous solution alkali cleaning, 5 ~ 10min, with water cleaning, dry up with acetone cleaning, gas.
3. the preparation method of a kind of anti-bacteria stainless steel material of Ionic Liquid Modified as claimed in claim 1, is characterized in that in step 2) in, described hydrogen peroxide adopts mass percentage concentration to be the hydrogen peroxide of 30%.
4. the preparation method of a kind of anti-bacteria stainless steel material of Ionic Liquid Modified as claimed in claim 1, is characterized in that in step 2) in, described sulfuric acid adopts the commercially available vitriol oil.
5. the preparation method of a kind of anti-bacteria stainless steel material of Ionic Liquid Modified as claimed in claim 1, is characterized in that in step 2) in, the volume ratio of hydrogen peroxide and sulfuric acid is (3 ~ 7): 1.
6. the preparation method of a kind of anti-bacteria stainless steel material of Ionic Liquid Modified as claimed in claim 1, is characterized in that in step 2) in, the described hydroxylated time is 20 ~ 60min.
7. the preparation method of a kind of anti-bacteria stainless steel material of Ionic Liquid Modified as claimed in claim 1, is characterized in that in step 3) in, described γ-mercaptopropyl trimethoxysilane adopts volumetric molar concentration to be the γ-mercaptopropyl trimethoxysilane of 20 ~ 80mM; The time of described stainless steel surface γ-mercaptopropyl trimethoxysilane self-assembly is 6 ~ 12h.
8. the preparation method of a kind of anti-bacteria stainless steel material of Ionic Liquid Modified as claimed in claim 1, is characterized in that in step 4) in, the described HCl aqueous solution adopts volumetric molar concentration to be the HCl aqueous solution of 0.1 ~ 0.05M.
9. the preparation method of a kind of anti-bacteria stainless steel material of Ionic Liquid Modified as claimed in claim 1, is characterized in that in step 4) in, the time of described hydrolysis is 6 ~ 12h; Ethanol and washed with de-ionized water are used in described cleaning successively; The condition of described solidification is 100 ~ 105 DEG C of solidification 3 ~ 8h.
10. the preparation method of a kind of anti-bacteria stainless steel material of Ionic Liquid Modified as claimed in claim 1, it is characterized in that in step 4) in, in described ionic liquid monomer 1-thiazolinyl-3-alkyl imidazole salt, 3-long alkyl chains is C4 ~ C18,1-alkenylalkyl carbon chain lengths is C1 ~ C12, and negatively charged ion is Br
-, BF
4 -, PF
6 -; Described initiator adopts Diisopropyl azodicarboxylate AIBN, and the consumption of initiator is 0.1% ~ 1% of ionic liquid monomer 1-thiazolinyl-3-alkyl imidazole salt by mass percentage; Described solvent is selected from the one in trichloromethane, dimethyl formamide, dimethyl sulfoxide (DMSO), methyl alcohol, ethanol; In described oil bath, reaction conditions is at 50 ~ 70 DEG C of reaction 6 ~ 15h; Described cleaning is cleaning 3 times.
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