CN106928797B - A kind of reversible selfreparing antimicrobial acrylic coating, preparation and self-repair method - Google Patents
A kind of reversible selfreparing antimicrobial acrylic coating, preparation and self-repair method Download PDFInfo
- Publication number
- CN106928797B CN106928797B CN201710230353.4A CN201710230353A CN106928797B CN 106928797 B CN106928797 B CN 106928797B CN 201710230353 A CN201710230353 A CN 201710230353A CN 106928797 B CN106928797 B CN 106928797B
- Authority
- CN
- China
- Prior art keywords
- preparation
- glycine betaine
- selfreparing
- sulfonyl
- reversible
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Plant Pathology (AREA)
- Paints Or Removers (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
Abstract
The invention discloses a kind of reversible selfreparing antimicrobial acrylic coating, preparation and self-repair methods.Methyl methacrylate, butyl acrylate, sulfonyl glycine betaine methacrylate, acetoacetate methacrylic acid glycol ester are added in alcoholic solvent, free radical polymerization is caused by azodiisobutyronitrile, obtains linear propylene's acid resin.Linear propylene's acid resin and amino-containing hyperbranched polyorganosiloxane are dissolved in alcoholic solvent, substrate surface is coated on, obtains a kind of reversible selfreparing antimicrobial acrylic coating after dry.The characteristics of reversible reaction can occur at room temperature for vinylamine ester bond between the present invention utilizes and the amino that hyperbranched polyorganosiloxane end is rich in; it realizes efficient, the mild selfreparing of coating, and assigns acrylic acid coatings excellent antibiotic property with safe and nontoxic and nonspecific sulfonyl glycine betaine.Product applicability provided by the invention is good, practical；Preparation method has the characteristics that raw material sources are wide, simple process, environmental protection.
Description
Technical field
The present invention relates to a kind of polymer coating and preparation method thereof, in particular to a kind of reversible selfreparing antimicrobial acrylic
Coating, preparation and its self-repair method, belong to technical field of polymer materials.
Background technique
Surface microorganism absorption and the Biofilm contamination generated therewith are to house decoration, medical facilities, food/pharmaceutical
The safety and sanitation situation of the indoor scenarios such as production generates grave danger.In general, the formation initial stage of biomembrane is by the non-spy of bacterium
What anisotropic reversible adsorption was formed in matrix surface, after bacterial adsorption generates exocellular polysaccharide formation three-dimensional structure, biomembrane
It is just difficult to remove.If matrix surface covers one layer of antimicrobial coating, the absorption of bacterium may refrain from the initial stage, it can be from the root
It effectively prevent the formation of biomembrane.
Acrylic resin is that the widely used environment-friendly coating in building decoration, the acrylic acid with anti-microbial property apply at present
Layer is just being widely studied and is largely using.Currently, mainly passing through in production with antimicrobial acrylic coating common in scientific research
The mode for adding antibacterial agent and resin physical blending is made, and the antibacterial agent used is many kinds of, respectively there is advantage and disadvantage.Such as metal
And its esters (such as gold, silver, copper and zinc) is common antibacterial agent (referring to document: Simchi, A., et al.Recent
progress in inorganic and composite coatings with bactericidal capability for
orthopaedic applications.Nanomedicine:Nanotechnology,Biology and Medicine,
2011,7 (1): 22-39), have the advantages that high activity, long-term effect, but there is a problem of that at high cost and toxicity is big.It is organic anti-
Microbial inoculum is although rapid-action, but poor to light heat stability, and working life is short, such as isothiazolone, phenols, halogen amine not only have
Poison, there are also carcinogenic risks (referring to document: Kocer, H.B.Residual disinfection with N-halamine
Based antimicrobial paints.Progress in Organic Coatings, 2012,74 (1): 100-105)；
Poly bis guanidine then decompose and deliquesce by toxic easy illumination；It is easily decomposed under triclosan itself is nontoxic but illumination and generates more chlorine dioxins and have
Noxious material is (referring to document: Orhan, M., et al.Improving the antibacterial activity of
cotton fabrics finished with triclosan by the use of 1,2,3,4-
butanetetracarboxylic acid and citric acid. Journal of Applied Polymer
Science, 2009,111 (3): 1344-1352).Quaternary ammonium salt has the advantages that hypotoxicity, long-term effect, but per se with just
Charge, being easy absorption dust and microorganism remains causes anti-microbial property to decline to a great extent, the emulsifier and detergent with anionic
Also there is conflict.Chitosan can be used as nontoxic biomass antibacterial agent, but it is sensitive to pH, can only use and make in acid condition
It is short (referring to document: Raafat, D.and H.-G.Sahl. Chitosan and its antimicrobial with the service life
Potential-a critical literature survey. Microbial Biotechnology, 2009,2 (2):
186-201).Therefore, still lack a kind of nontoxic antimicrobial acrylic coating with high activity, long-term effect at present.
On the other hand, antimicrobial coating is in actual use often because situations such as rubbing, colliding causes metope to apply
It is even damaged that layer generates micro-crack, scratch.This weakens the dimensional stability and mechanical strength of coating to varying degrees, more sternly
Weight is that these slight cracks for the breeding and propagation of microorganism provide good living space.In order to prevent trouble before it happens, in slight crack
Generation initial stage just repairs micro-crack, prevents its extension, extends the service life of coating, the antimicrobial acrylic with self-healing properties
Coating is just causing more and more to pay close attention to.
Document " Antifouling and antibacterial hydrogel coatings with self-
Healing properties based on a dynamic disulfide exchange reaction " (Yang, W.
J., et al. Polymer Chemistry, 2015,6 (39): 7027-7035.) it discloses and passes through in stainless steel surface
Light-initiated mode obtains the technical solution of the acrylic hydrogel film containing cystine linkage, which passes through side chain quaternary ammonium salt
Antibacterial action has the antibacterial effect greater than 86% to Escherichia coli；The reversible of the cystine linkage of bridge linking effect is played between main chain simultaneously
Fracture-addition makes aquagel membrane that can repair scratch within 1h.However, as previously mentioned, the anti-microbial property of quaternary ammonium salt can be with
Declined to a great extent using the time, while aquagel membrane limited mechanical strength, be not appropriate for for house decoration, medical facilities, food/
The indoor scenarios such as pharmaceutical production.Other aquagel membranes with antibacterial effect similarly there is a problem of similar.
In conclusion researching and developing the antibacterial propylene that a kind of reversible self-repair efficiency is high, repairing condition is mild and tensile strength is high
Acid coated is the project with major application value.
Summary of the invention
That in view of the deficiencies of the prior art, the present invention provides a kind of self-repair efficiencies is high, repairing condition is mild, and has safety
Reversible selfreparing antimicrobial acrylic coating, preparation and the self-repair method of long acting antibiotic effect.
In order to achieve the above objectives, the technical scheme adopted by the invention is that providing a kind of reversible selfreparing antimicrobial acrylic painting
The preparation method of layer, includes the following steps:
(1) under inert gas protection, by mass, by 10 parts of gamma-aminopropyl-triethoxy-silanes, 1~1.5 part it is water-soluble
In 10~20 parts of alcoholic solvents, it is uniformly mixed；4~6h, institute are reacted under conditions of inert gas shielding, temperature are 60~80 DEG C
After solution is cooled to room temperature, alcoholic solvent is evaporated off, obtained colourless liquid is amino-containing hyperbranched polyorganosiloxane；
(2) at room temperature, 16 parts of methacrylic acid 2- (dimethylamino) ethyl esters and 12~15 parts of 1,3-propane sultone are molten
In 100~200 parts of alkyl chlorides, after mixing evenly, 60~80 DEG C are warming up to the reaction was continued 3~6h, gained mixed liquor is cooled to
It is filtered after room temperature, obtained white powder is sulfonyl glycine betaine methacrylate；
(3) under inert gas protection, by 2.5 parts of methyl methacrylates, 4.5 parts of butyl acrylates, 2 parts of sulfonyls
Glycine betaine methacrylate, 1 part of acetoacetate methacrylic acid glycol ester and 0.3 part of azodiisobutyronitrile are dissolved in 20~30
In part alcoholic solvent, 2~4h is polymerize under conditions of temperature is 60~80 DEG C, obtains mixed liquor；Mixed liquor is added to 50~60
In part n-hexane, agitation and filtration, filter cake is dried in vacuo after being washed with alcoholic solvent, and obtained solid is the line of the glycine betaine containing sulfonyl
Property acrylic resin；
(4) under conditions of temperature is 50~60 DEG C, linear the third of the glycine betaine containing sulfonyl that 6 parts of steps (3) are obtained
The amino-containing hyperbranched polyorganosiloxane that olefin(e) acid resin and 0.2~0.6 part of step (1) obtain is dissolved in 20~30 parts of alcoholic solvents
In, it is uniformly mixed, obtains colourless transparent solution；
(5) solution for obtaining step (4) is coated on substrate surface, obtains a kind of reversible selfreparing antibacterial third after dry
Olefin(e) acid coating.
In above-mentioned preparation method, the inert gas is one kind or their any combination of nitrogen, argon gas.
The alcoholic solvent be one of methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, isobutanol or they
Any combination.
The alkyl chloride is one of methylene chloride, chloroform, 1,2- methylene chloride or their any group
It closes.
The substrate is metal material, inorganic non-metallic material or organic material.
The metal material is aluminium alloy plate；The inorganic non-metallic material is glass；The organic material is
Polytetrafluoroethylene (PTFE).
Technical solution of the present invention further includes a kind of reversible selfreparing antimicrobial acrylic coating that the method that is prepared as described above obtains.
The self-repair method for a kind of reversible selfreparing antimicrobial acrylic coating that technical solution of the present invention provides, by impaired painting
Layer selfreparing under conditions of temperature is 60~120 DEG C is handled 8~24 hours.
Compared with prior art, the beneficial effect that the present invention obtains is:
1, acrylic acid coatings provided by the invention have both reversible selfreparing and anti-microbial property, and vinylamine ester bond exists between it is utilized
The characteristics of reversible reaction can occur at room temperature, is greater than the excellent of 94%, repairing condition mild (60 DEG C, 8h) with self-repair efficiency
Gesture.
2, the present invention is using sulfonyl glycine betaine as antibacterial components, compared with tradition adds blending type antibacterial agent, has non-spy
Anisotropic and nontoxic advantage, while sulfonyl glycine betaine accesses acrylic acid tree terminal double bond in a manner of radical copolymerization
In rouge main chain, the problem of overcoming the incident exudation of addition blending type antibacterial agent or dissolve out, the antibacterial with safety and effectivity is imitated
Fruit.
3, the hyperbranched polyorganosiloxane that uses of the present invention has the characteristics that chain entanglement is few, segment easy glide, while end richness
It containing amino, ensure that a chemical balance for vinylamine ester bond is mobile to bonding direction, promote coating and micro-crack, scratch etc. occurs
High efficiency selfreparing behavior when destruction.
4, hyperbranched polyorganosiloxane provided by the invention, linear propylene's acid resin and selfreparing antimicrobial coating only need to be with second
Alcohol is that solvent can prepare, and has good craftsmanship and environmental protection characteristic.
5, the preparation method of reversible selfreparing antimicrobial coating provided by the invention has that raw material sources are wide, simple process,
Product has the characteristics that applicability is good, practical.
Detailed description of the invention
Fig. 1 is the hydrogen nuclear magnetic resonance of the amino-containing hyperbranched polyorganosiloxane in end (HPSi) prepared by the embodiment of the present invention 1
Spectrum (1H-NMR).
Fig. 2 is the nuclear magnetic resonance silicon of the amino-containing hyperbranched polyorganosiloxane in end (HPSi) prepared by the embodiment of the present invention 1
Spectrum (29Si-NMR).
Fig. 3 be the embodiment of the present invention 1 prepare sulfonyl glycine betaine methacrylate nuclear magnetic resonance spectroscopy (1H-
NMR).
Fig. 4 is that linear propylene's acid resin of the glycine betaine containing sulfonyl prepared by the embodiment of the present invention 1 and reversible selfreparing resist
The infrared spectrum of bacterium acrylic acid coatings.
Fig. 5 is that linear propylene's acid resin of the glycine betaine containing sulfonyl prepared by the embodiment of the present invention 1 and reversible selfreparing resist
The thermogravimetric curve of bacterium acrylic acid coatings.
Fig. 6 is that linear propylene's acid resin of the glycine betaine containing sulfonyl prepared by the embodiment of the present invention 1 and reversible selfreparing resist
The tensile stress-strain curve of bacterium acrylic acid coatings.
Fig. 7 is that linear propylene's acid resin of the glycine betaine containing sulfonyl prepared by the embodiment of the present invention 1 and reversible selfreparing resist
The dynamic mechanical curve of bacterium acrylic acid coatings.
Fig. 8 is that the digital of the self-repair procedure of reversible selfreparing antimicrobial acrylic coating prepared by the embodiment of the present invention 1 is shone
Piece.
Fig. 9 is that reversible selfreparing antimicrobial acrylic coating prepared by the embodiment of the present invention 1 is surveyed after different reparation durations
The load-deformation curve of examination.
Figure 10 is that the digital of the antibacterial effect of reversible selfreparing antimicrobial acrylic coating prepared by the embodiment of the present invention 1 is shone
Piece.
Specific embodiment
With reference to the accompanying drawings and examples, technical solution of the present invention will be further described.
Embodiment 1
1) preparation of the amino-containing hyperbranched polyorganosiloxane in end (being denoted as HPSi)
Under nitrogen protection, by the gamma-aminopropyl-triethoxy-silane of 44.0g (KH550) and 4.3g it is water-soluble in
4h is reacted in 40.0mL ethyl alcohol and at 60 DEG C.After acquired solution is cooled to room temperature, alcoholic solvent is evaporated off, obtains colourless liquid, i.e.,
The amino-containing hyperbranched polyorganosiloxane in end (HPSi), nuclear magnetic resonance spectroscopy and nuclear magnetic resonance silicon compose respectively referring to attached drawing 1 and
2。
2) preparation of sulfonyl glycine betaine methacrylate
At room temperature, 15.7g methacrylic acid 2- (dimethylamino) ethyl ester and 12.2g1,3- propane sultone are dissolved in
In 100mL1,2- dichloroethanes after mixing evenly, 60 DEG C are warming up to the reaction was continued 3h.Mistake after gained mixed liquor is cooled to room temperature
Filter, obtains white powder, i.e. sulfonyl glycine betaine methacrylate, nuclear magnetic resonance spectroscopy is shown in attached drawing 3.
3) preparation of linear propylene's acid resin of the glycine betaine containing sulfonyl
Under nitrogen protection, by 2.5g methyl methacrylate, 4.5g butyl acrylate, 2.0g sulfonyl glycine betaine methyl
Acrylate, 1.0g acetoacetate methacrylic acid glycol ester and 0.3g azodiisobutyronitrile are dissolved in 20mL ethyl alcohol, and
It polymerize 2h at 70 DEG C.Gained mixed liquor is added in 50mL n-hexane, agitation and filtration, is dried in vacuo after filter cake ethanol washing, institute
Linear propylene's acid resin that solid is the glycine betaine containing sulfonyl is obtained, infrared spectrum, thermogravimetric curve, tensile stress-strain are bent
Line, dynamic mechanical curve are shown in attached drawing 4,5,6 and 7 respectively.
4) preparation of reversible selfreparing antimicrobial acrylic coating
The linear propylene's acid resin and 0.4gHPSi of 6g glycine betaine containing sulfonyl are dissolved in 20mL ethyl alcohol at 50 DEG C, mixed
Uniformly, colourless transparent solution is obtained.
Obtained solution is coated on ptfe surface, levelling obtains reversible selfreparing antibacterial propylene after dry
Acid coated, coating layer thickness 0.3mm, wherein the content of HPSi is 6.3wt%.Its infrared spectrum, thermogravimetric curve, tensile stress-
Strain curve, dynamic mechanical curve, antibacterial effect digital photograph see attached drawing 4,5,6,7 and 10 respectively.
5) self-repair method of reversible selfreparing antimicrobial acrylic coating
By damaged coating, selfreparing is handled 24 hours under conditions of temperature is 60 DEG C.The digital photograph of its self-repair procedure
Attached drawing 8 and 9 is seen respectively with the load-deformation curve tested after different reparation durations.
Referring to attached drawing 1, it be the amino-containing hyperbranched polyorganosiloxane in end manufactured in the present embodiment (HPSi) nuclear-magnetism it is total
Vibration hydrogen spectrum (1H-NMR).As seen from the figure, the characteristic peak at δ=1.21ppm is Si-O-CH2CH3The H of upper methyl (b), but its H
C in any C(figure on number and aminopropyl, d or e) on the ratio between the number of H be 3:2, the corresponding 9:2 of far smaller than KH550, explanation
Hydrolytic condensation generates Si-O-Si between KH550.
Referring to attached drawing 2, it be the amino-containing hyperbranched polyorganosiloxane in end manufactured in the present embodiment (HPSi) nuclear-magnetism it is total
Vibration silicon spectrum (29Si-NMR).Wherein D, L, T have respectively represented the branching chain link of hyperbranched siloxane, linear chain link and sealing end chain link.
It can be found that the peak D is significantly stronger than the peak L and the peak T from figure, illustrates that branching chain link is generally existing in HPSi, further demonstrate
KH550 monomer has been fully hydrolyzed condensation.According to the corresponding integral area of D in figure and L, branch is calculated using such as following formula (1) formula
The value of change degree DB:
(1)
By calculating it is found that the DB of HPSi is 0.86, close to DB=1 of dendrimer, illustrate the molecule knot of HPSi
Structure is close with dendrimer, has lower viscosity and preferable dissolubility, and surface is rich in active amino, has high living
Property with reactivity.
Referring to attached drawing 3, it is the nuclear magnetic resonance spectroscopy of sulfonyl glycine betaine methacrylate manufactured in the present embodiment
(1H-NMR).Each H in each peak counter structure formula.Wherein the characteristic peak at δ=6.09ppm and δ=5.77-5.72ppm (a and
It b) is the H on C=C.Characteristic peak (f) at δ=3.09ppm is and N+Two connected-CH3On six H, and methacrylic acid
Two-CH being connected in 2- (dimethylamino) ethyl ester with N3On H be usually located at δ=2.30ppm, the two compare there are about
The chemical shift difference of 0.79ppm.This is because script-N (CH3)2In N be electroneutral, be changed into the N of positive charge+Electronegativity afterwards
Increase, leads to-CH3Chemical shift it is mobile to low field, this directly demonstrates sulfonyl glycine betaine methacrylate and has succeeded
Preparation.
Referring to attached drawing 4, it is that linear propylene's acid resin of the glycine betaine manufactured in the present embodiment containing sulfonyl is reviewed one's lessons by oneself with reversible
The infrared spectrum of multiple antimicrobial acrylic coating.Wherein, 3000cm-1Above without obvious absorption peaks, illustrate the glycine betaine containing sulfonyl
C=C is free of in linear propylene's acid resin and reversible selfreparing antimicrobial acrylic coating, i.e., unpolymerized acrylate monomer is
Through being removed clean.2800 to 3000cm-1Between characteristic peak be-CH3(2960cm-1And 2870cm-1) and-CH2(2920cm-1And 2850cm-1), 1730cm-1The sharp peak at place is the characteristic peak of C=O, and 1038cm-1The absorption peak at place is the SO in MESA3 -
Characteristic peak.Compared with linear propylene's acid resin of the glycine betaine containing sulfonyl, reversible selfreparing antimicrobial acrylic coating it is infrared
Spectrum is in 1650cm-1And 1605cm-1New characteristic peak is generated, is illustrated after HPSi is added, reversible selfreparing antimicrobial acrylic applies
It is produced in layer using vinylamine ester covalent bond between reversible as the reticular structure of crosslinking points.
Referring to attached drawing 5, it is that linear propylene's acid resin of the glycine betaine manufactured in the present embodiment containing sulfonyl is reviewed one's lessons by oneself with reversible
The thermogravimetric curve of multiple antimicrobial acrylic coating.Wherein, the initial pyrolyzation of linear propylene's acid resin of the glycine betaine containing sulfonyl
Temperature is 266 DEG C, and the initial pyrolyzation temperature of reversible selfreparing antimicrobial acrylic coating is 250 DEG C.This is because being added
The reversible vinylamine ester bond bond energy generated after HPSi is less than the bond energy of carbonyl, is heated caused by being easier to decompose.But it is reversible
Carbon left at 800 DEG C of selfreparing antimicrobial acrylic coating is 6.99wt%, sour compared to the linear propylene of the glycine betaine containing sulfonyl
The carbon left (0.58wt%) of resin under the same conditions has obvious rising, illustrates as the temperature rises, reversible selfreparing antibacterial
The layer of charcoal of acrylic acid coatings has better thermal stability.
Referring to attached drawing 6, it is that linear propylene's acid resin of the glycine betaine manufactured in the present embodiment containing sulfonyl is reviewed one's lessons by oneself with reversible
The tensile stress-strain curve of multiple antimicrobial acrylic coating.According to as shown in the figure, the tensile strength that both can calculate separately out,
Young's modulus and toughness (integral area under load-deformation curve).Linear propylene's acid resin of the glycine betaine containing sulfonyl resists
Tensile strength and Young's modulus are only 1.71MPa and 61.54MPa, and toughness is 1.73MPa.In contrast, reversible selfreparing antibacterial
The tensile strength and Young's modulus of acrylic acid coatings improve 10.14 times and 6.97 times respectively, and toughness then improves 3.26 times.
These data explanation, reversible selfreparing antimicrobial acrylic coating have more compared to linear propylene's acid resin of the glycine betaine containing sulfonyl
For tough mechanical property, it is suitable for the indoor scenarios such as house decoration, medical facilities, food/pharmaceutical production.
Referring to attached drawing 7, it is that linear propylene's acid resin of the glycine betaine manufactured in the present embodiment containing sulfonyl is reviewed one's lessons by oneself with reversible
The dynamic mechanical curve of multiple antimicrobial acrylic coating.Wherein glass transition temperature of the peak temperature of Tan δ as the two.Contain
The glass transition temperature of linear propylene's acid resin of sulfonyl glycine betaine is 24 DEG C, therefore is in elastomeric state at room temperature, with it
The phenomenon that tensile stress-strain curve is presented is consistent.And reversible selfreparing antimicrobial acrylic coated glass transition temperature point
57 DEG C are not risen to, is in glassy state at room temperature, and sub-chain motion is limited, while the cross-linked structure that HPSi formation is added also leads to it
Rigidity reinforced, corresponding tensile strength are substantially increased with Young's modulus.
Referring to attached drawing 8, it is the number of the self-repair procedure of reversible selfreparing antimicrobial acrylic coating manufactured in the present embodiment
Code photo.The self-healing properties of coating are tested by petrographic microscope, the surface scratch after observing its different repair time
Pattern variation.First it cut the cross wound that a road width is 40 μm in coating surface with scalpel, such as black cross in Fig. 8 (a)
Painting after cutting is placed in 60 DEG C of baking oven and carries out selfreparing by region.Fig. 8 (b) is that coating repairs the photo after 8h, cross
Wound has narrowed, and lighttight black region has shoaled；Fig. 8 (c) is that coating repairs the photo after 16h, and cross wound is further
It reduces, and there is the opaque black region in part to restore the transparence to before being damaged；Fig. 8 (d) is the photograph after coating is repaired for 24 hours
Piece, cross wound pattern have restored to transparent, and leave one of scar after surface is similar to human skin healing.Fig. 8 observation
As a result it sufficiently proves, reversible selfreparing antimicrobial acrylic coating provided by the invention reviews one's lessons by oneself reactivation with good at 60 DEG C
Power.And there is similar T in document disclosed in the prior artgThe reparation temperature of acrylic acid coatings be greater than 80 DEG C, repair time
Greater than 18h, therefore, the selfreparing of reversible selfreparing antimicrobial acrylic coating prepared by the present invention has mild advantage.
Referring to attached drawing 9, it is reversible selfreparing antimicrobial acrylic coating manufactured in the present embodiment by different reparation durations
The load-deformation curve tested afterwards.As can be seen that with the extension of repair time, the tensile strength of coating, elongation at break and
Toughness is gradually brought to original state.Tensile strength, fracture after reversible 60 DEG C of selfreparing antimicrobial acrylic coating reparations for 24 hours
Elongation and toughness are restored respectively to the 96.77% of initial value, 98.08% and 94.32%.
Referring to attached drawing 10, it is the number of the antibacterial effect of reversible selfreparing antimicrobial acrylic coating manufactured in the present embodiment
Photo.By colony counting method, using gram-positive staphylococcus aureus and gram-negative Escherichia coli as sample
Bacterium assesses the anti-microbial property of coating.The difference of clump count on agar medium can be obviously observed from attached drawing 10.Compared to sky
White glass (figure a is Escherichia coli, and figure c is staphylococcus aureus), is covered with the examination of reversible selfreparing antimicrobial acrylic coating
Sample clump count significantly reduces (figure b is Escherichia coli, and figure d is staphylococcus aureus), to staphylococcus aureus and large intestine
The antibiotic rate of bacillus is all larger than 95%, has significant anti-microbial property.
Embodiment 2
1) preparation of the amino-containing hyperbranched polyorganosiloxane in end (being denoted as HPSi)
Under protection of argon gas, by the gamma-aminopropyl-triethoxy-silane of 44.0g (KH550) and 4.3g it is water-soluble in
4h is reacted in 40.0mL ethyl alcohol and at 60 DEG C.After acquired solution is cooled to room temperature, alcoholic solvent is evaporated off, obtains colourless liquid, i.e.,
The amino-containing hyperbranched polyorganosiloxane in end (HPSi).
2) preparation of sulfonyl glycine betaine methacrylate
At room temperature, 15.7g methacrylic acid 2- (dimethylamino) ethyl ester and 13.4g1,3- propane sultone are dissolved in
In 100mL1,2- dichloroethanes after mixing evenly, 60 DEG C are warming up to the reaction was continued 3h.Mistake after gained mixed liquor is cooled to room temperature
Filter, obtains white powder, i.e. sulfonyl glycine betaine methacrylate.
3) preparation of linear propylene's acid resin of the glycine betaine containing sulfonyl
Under protection of argon gas, by 2.5g methyl methacrylate, 4.5g butyl acrylate, 2.0g sulfonyl glycine betaine methyl
Acrylate, 1.0g acetoacetate methacrylic acid glycol ester and 0.3g azodiisobutyronitrile are dissolved in 20mL ethyl alcohol, and
It polymerize 2h at 70 DEG C.Gained mixed liquor is added in 50mL n-hexane, agitation and filtration, is dried in vacuo after filter cake ethanol washing, institute
Obtain linear propylene's acid resin that solid is the glycine betaine containing sulfonyl.
4) preparation of reversible selfreparing antimicrobial acrylic coating
The HPSi of linear propylene's acid resin of 6g glycine betaine containing sulfonyl and 0.4g is dissolved in 20mL ethyl alcohol at 55 DEG C, is mixed
It closes uniformly, obtains colourless transparent solution；
Obtained solution is coated on aluminium alloy plate surface, levelling obtains reversible selfreparing antimicrobial acrylic after dry
Coating.
5) self-repair method of reversible selfreparing antimicrobial acrylic coating
By damaged coating, selfreparing is handled 24 hours under conditions of temperature is 80 DEG C.
Embodiment 3
1) preparation of the amino-containing hyperbranched polyorganosiloxane in end (being denoted as HPSi)
Nitrogen and argon gas it is mixed gas protected under, by the gamma-aminopropyl-triethoxy-silane (KH550) of 44.0g with
The water-soluble of 4.3g reacts 4h in 40.0mL ethyl alcohol and at 60 DEG C.After acquired solution is cooled to room temperature, alcoholic solvent is evaporated off, obtains
The amino-containing hyperbranched polyorganosiloxane of colourless liquid, i.e. end (HPSi).
2) preparation of sulfonyl glycine betaine methacrylate
At room temperature, 15.7g methacrylic acid 2- (dimethylamino) ethyl ester and 15.0g1,3- propane sultone are dissolved in
In 100mL1,2- dichloroethanes after mixing evenly, 60 DEG C are warming up to the reaction was continued 3h.Mistake after gained mixed liquor is cooled to room temperature
Filter, obtains white powder, i.e. sulfonyl glycine betaine methacrylate.
3) preparation of linear propylene's acid resin of the glycine betaine containing sulfonyl
Under the mixed gas of nitrogen and argon gas, by 2.5g methyl methacrylate, 4.5g butyl acrylate, 2.0g sulphonyl
Base glycine betaine methacrylate, 1.0g acetoacetate methacrylic acid glycol ester and 0.3g azodiisobutyronitrile are dissolved in 20mL
In ethyl alcohol, and it polymerize 2h at 70 DEG C.Gained mixed liquor is added in 50mL n-hexane, agitation and filtration, after filter cake ethanol washing
Vacuum drying, obtained solid are linear propylene's acid resin of the glycine betaine containing sulfonyl.
4) preparation of reversible selfreparing antimicrobial acrylic coating
The HPSi of linear propylene's acid resin of 6g glycine betaine containing sulfonyl and 0.4g is dissolved in 20mL ethyl alcohol at 60 DEG C, is mixed
It closes uniformly, obtains colourless transparent solution；
Obtained solution is coated on glass surface, levelling obtains reversible selfreparing antimicrobial acrylic coating after dry.
5) self-repair method of reversible selfreparing antimicrobial acrylic coating
By damaged coating, selfreparing is handled 24 hours under conditions of temperature is 120 DEG C.
Embodiment 4
1) preparation of the amino-containing hyperbranched polyorganosiloxane in end (being denoted as HPSi)
Under nitrogen protection, by the gamma-aminopropyl-triethoxy-silane of 44.0g (KH550) and 5.1g it is water-soluble in
4h is reacted in 40.0mL ethyl alcohol and at 60 DEG C.After acquired solution is cooled to room temperature, alcoholic solvent is evaporated off, obtains colourless liquid, i.e.,
The amino-containing hyperbranched polyorganosiloxane in end (HPSi).
2) preparation of sulfonyl glycine betaine methacrylate
At room temperature, 15.7g methacrylic acid 2- (dimethylamino) ethyl ester and 12.2g1,3- propane sultone are dissolved in
In 150mL1,2- dichloroethanes after mixing evenly, 60 DEG C are warming up to the reaction was continued 3h.Mistake after gained mixed liquor is cooled to room temperature
Filter, obtains white powder, i.e. sulfonyl glycine betaine methacrylate.
3) preparation of linear propylene's acid resin of the glycine betaine containing sulfonyl
Under nitrogen protection, by 2.5g methyl methacrylate, 4.5g butyl acrylate, 2.0g sulfonyl glycine betaine methyl
Acrylate, 1.0g acetoacetate methacrylic acid glycol ester and 0.3g azodiisobutyronitrile are dissolved in 25mL ethyl alcohol, and
It polymerize 2h at 70 DEG C.Gained mixed liquor is added in 50mL n-hexane, agitation and filtration, is dried in vacuo after filter cake ethanol washing, institute
Obtain linear propylene's acid resin that solid is the glycine betaine containing sulfonyl.
4) preparation of reversible selfreparing antimicrobial acrylic coating
The HPSi of linear propylene's acid resin of 6g glycine betaine containing sulfonyl and 0.2g is dissolved in 20mL ethyl alcohol at 50 DEG C, is mixed
It closes uniformly, obtains colourless transparent solution；
Obtained solution is coated on ptfe surface, levelling obtains reversible selfreparing antibacterial propylene after dry
It is acid coated.
5) self-repair method of reversible selfreparing antimicrobial acrylic coating
By damaged coating, selfreparing is handled 16 hours under conditions of temperature is 120 DEG C.
Embodiment 5
1) preparation of the amino-containing hyperbranched polyorganosiloxane in end (being denoted as HPSi)
Under nitrogen protection, by the gamma-aminopropyl-triethoxy-silane of 44.0g (KH550) and 6.4g it is water-soluble in
4h is reacted in 40.0mL ethyl alcohol and at 60 DEG C.After acquired solution is cooled to room temperature, alcoholic solvent is evaporated off, obtains colourless liquid, i.e.,
The amino-containing hyperbranched polyorganosiloxane in end (HPSi).
2) preparation of sulfonyl glycine betaine methacrylate
At room temperature, 15.7g methacrylic acid 2- (dimethylamino) ethyl ester and 12.2g1,3- propane sultone are dissolved in
In 200mL1,2- dichloroethanes after mixing evenly, 60 DEG C are warming up to the reaction was continued 3h.Mistake after gained mixed liquor is cooled to room temperature
Filter, obtains white powder, i.e. sulfonyl glycine betaine methacrylate.
3) preparation of linear propylene's acid resin of the glycine betaine containing sulfonyl
Under nitrogen protection, by 2.5g methyl methacrylate, 4.5g butyl acrylate, 2.0g sulfonyl glycine betaine methyl
Acrylate, 1.0g acetoacetate methacrylic acid glycol ester and 0.3g azodiisobutyronitrile are dissolved in 30mL ethyl alcohol, and
It polymerize 2h at 70 DEG C.Gained mixed liquor is added in 50mL n-hexane, agitation and filtration, is dried in vacuo after filter cake ethanol washing, institute
Obtain linear propylene's acid resin that solid is the glycine betaine containing sulfonyl.
4) preparation of reversible selfreparing antimicrobial acrylic coating
The HPSi of linear propylene's acid resin of 6g glycine betaine containing sulfonyl and 0.3g is dissolved in 20mL ethyl alcohol at 50 DEG C, is mixed
It closes uniformly, obtains colourless transparent solution；
Obtained solution is coated on glass surface, levelling obtains reversible selfreparing antimicrobial acrylic coating after dry.
5) self-repair method of reversible selfreparing antimicrobial acrylic coating
By damaged coating, selfreparing is handled 8 hours under conditions of temperature is 120 DEG C.
Embodiment 6
1) preparation of the amino-containing hyperbranched polyorganosiloxane in end (being denoted as HPSi)
Under nitrogen protection, by the gamma-aminopropyl-triethoxy-silane of 44.0g (KH550) and 4.3g it is water-soluble in
4h is reacted in 60.0mL ethyl alcohol and at 60 DEG C.After acquired solution is cooled to room temperature, alcoholic solvent is evaporated off, obtains colourless liquid, i.e.,
The amino-containing hyperbranched polyorganosiloxane in end (HPSi).
2) preparation of sulfonyl glycine betaine methacrylate
At room temperature, 15.7g methacrylic acid 2- (dimethylamino) ethyl ester and 12.2g1,3- propane sultone are dissolved in
In 100mL methylene chloride after mixing evenly, 60 DEG C are warming up to the reaction was continued 3h.Gained mixed liquor filters after being cooled to room temperature, and obtains
To white powder, i.e. sulfonyl glycine betaine methacrylate.
3) preparation of linear propylene's acid resin of the glycine betaine containing sulfonyl
Under nitrogen protection, by 2.5g methyl methacrylate, 4.5g butyl acrylate, 2.0g sulfonyl glycine betaine methyl
Acrylate, 1.0g acetoacetate methacrylic acid glycol ester and 0.3g azodiisobutyronitrile are dissolved in 20mL methanol, and
It polymerize 2h at 70 DEG C.Gained mixed liquor is added in 50mL n-hexane, agitation and filtration, is dried in vacuo after filter cake ethanol washing, institute
Obtain linear propylene's acid resin that solid is the glycine betaine containing sulfonyl.
4) preparation of reversible selfreparing antimicrobial acrylic coating
The HPSi of linear propylene's acid resin of 6g glycine betaine containing sulfonyl and 0.5g is dissolved in 20mL ethyl alcohol at 50 DEG C, is mixed
It closes uniformly, obtains colourless transparent solution；
Obtained solution is coated on aluminium alloy plate surface, levelling obtains reversible selfreparing antimicrobial acrylic after dry
Coating.
5) self-repair method of reversible selfreparing antimicrobial acrylic coating
Using the self-repair method of embodiment 1.
Embodiment 7
1) preparation of the amino-containing hyperbranched polyorganosiloxane in end (being denoted as HPSi)
Under nitrogen protection, by the gamma-aminopropyl-triethoxy-silane of 44.0g (KH550) and 4.3g it is water-soluble in
4h is reacted in 80.0mL ethyl alcohol and at 60 DEG C.After acquired solution is cooled to room temperature, alcoholic solvent is evaporated off, obtains colourless liquid, i.e.,
The amino-containing hyperbranched polyorganosiloxane in end (HPSi).
2) preparation of sulfonyl glycine betaine methacrylate
At room temperature, 15.7g methacrylic acid 2- (dimethylamino) ethyl ester and 12.2g1,3- propane sultone are dissolved in
In 100mL chloroform after mixing evenly, 60 DEG C are warming up to the reaction was continued 3h.Gained mixed liquor filters after being cooled to room temperature, and obtains
To white powder, i.e. sulfonyl glycine betaine methacrylate.
3) preparation of linear propylene's acid resin of the glycine betaine containing sulfonyl
Under nitrogen protection, by 2.5g methyl methacrylate, 4.5g butyl acrylate, 2.0g sulfonyl glycine betaine methyl
Acrylate, 1.0g acetoacetate methacrylic acid glycol ester and 0.3g azodiisobutyronitrile are dissolved in 20mL normal propyl alcohol, and
It polymerize 2h at 70 DEG C.Gained mixed liquor is added in 50mL n-hexane, agitation and filtration, is dried in vacuo after filter cake ethanol washing,
Obtained solid is linear propylene's acid resin of the glycine betaine containing sulfonyl.
4) preparation of reversible selfreparing antimicrobial acrylic coating
The HPSi of linear propylene's acid resin of 6g glycine betaine containing sulfonyl and 0.6g is dissolved in 20mL ethyl alcohol at 50 DEG C, is mixed
It closes uniformly, obtains colourless transparent solution；
Obtained solution is coated on glass surface, levelling obtains reversible selfreparing antimicrobial acrylic coating after dry.
5) self-repair method of reversible selfreparing antimicrobial acrylic coating
Using the self-repair method of embodiment 1.
Embodiment 8
1) preparation of the amino-containing hyperbranched polyorganosiloxane in end (being denoted as HPSi)
Under nitrogen protection, by the gamma-aminopropyl-triethoxy-silane of 44.0g (KH550) and 4.3g it is water-soluble in
4h is reacted in 40.0mL methanol and at 60 DEG C.After acquired solution is cooled to room temperature, alcoholic solvent is evaporated off, obtains colourless liquid, i.e.,
The amino-containing hyperbranched polyorganosiloxane in end (HPSi).
2) preparation of sulfonyl glycine betaine methacrylate
At room temperature, 15.7g methacrylic acid 2- (dimethylamino) ethyl ester and 12.2g1,3- propane sultone are dissolved in 50mL
In methylene chloride and 50mL chloroform after mixing evenly, 60 DEG C are warming up to the reaction was continued 3h.Gained mixed liquor is cooled to room temperature
After filter, obtain white powder, i.e. sulfonyl glycine betaine methacrylate.
3) preparation of linear propylene's acid resin of the glycine betaine containing sulfonyl
Under nitrogen protection, by 2.5g methyl methacrylate, 4.5g butyl acrylate, 2.0g sulfonyl glycine betaine methyl
Acrylate, 1.0g acetoacetate methacrylic acid glycol ester and 0.3g azodiisobutyronitrile are dissolved in 20mL isopropanol, and
It polymerize 2h at 70 DEG C.Gained mixed liquor is added in 50mL n-hexane, agitation and filtration, is dried in vacuo after filter cake ethanol washing,
Obtained solid is linear propylene's acid resin of the glycine betaine containing sulfonyl.
4) preparation of reversible selfreparing antimicrobial acrylic coating
The HPSi of linear propylene's acid resin of 6g glycine betaine containing sulfonyl and 0.4g is dissolved in 25mL ethyl alcohol at 50 DEG C, is mixed
It closes uniformly, obtains colourless transparent solution；
Obtained solution is coated on aluminium alloy plate surface, levelling obtains reversible selfreparing antimicrobial acrylic after dry
Coating.
5) self-repair method of reversible selfreparing antimicrobial acrylic coating
By damaged coating, selfreparing is handled 22 hours under conditions of temperature is 80 DEG C.
Embodiment 9
1) preparation of the amino-containing hyperbranched polyorganosiloxane in end (being denoted as HPSi)
Under nitrogen protection, by the gamma-aminopropyl-triethoxy-silane of 44.0g (KH550) and 4.3g it is water-soluble in
4h is reacted in 40.0mL normal propyl alcohol and at 60 DEG C.After acquired solution is cooled to room temperature, alcoholic solvent is evaporated off, obtains colourless liquid,
That is the amino-containing hyperbranched polyorganosiloxane in end (HPSi).
2) preparation of sulfonyl glycine betaine methacrylate
At room temperature, 15.7g methacrylic acid 2- (dimethylamino) ethyl ester and 12.2g1,3- propane sultone are dissolved in 75mL
Methylene chloride and 75mL1 in 2- dichloroethanes are after mixing evenly warming up to 60 DEG C the reaction was continued 3h.Gained mixed liquor is cooled to
It is filtered after room temperature, obtains white powder, i.e. sulfonyl glycine betaine methacrylate.
3) preparation of linear propylene's acid resin of the glycine betaine containing sulfonyl
Under nitrogen protection, by 2.5g methyl methacrylate, 4.5g butyl acrylate, 2.0g sulfonyl glycine betaine methyl
Acrylate, 1.0g acetoacetate methacrylic acid glycol ester and 0.3g azodiisobutyronitrile are dissolved in 10mL methanol and 10mL second
In alcohol, and it polymerize 2h at 70 DEG C.Gained mixed liquor is added in 50mL n-hexane, agitation and filtration, true after filter cake ethanol washing
Sky is dry, and obtained solid is linear propylene's acid resin of the glycine betaine containing sulfonyl.
4) preparation of reversible selfreparing antimicrobial acrylic coating
The HPSi of linear propylene's acid resin of 6g glycine betaine containing sulfonyl and 0.4g is dissolved in 30mL ethyl alcohol at 50 DEG C, is mixed
It closes uniformly, obtains colourless transparent solution；
Obtained solution is coated on ptfe surface, levelling obtains reversible selfreparing antibacterial propylene after dry
It is acid coated.
5) self-repair method of reversible selfreparing antimicrobial acrylic coating
Using the self-repair method of embodiment 1.
Embodiment 10
1) preparation of the amino-containing hyperbranched polyorganosiloxane in end (being denoted as HPSi)
Under nitrogen protection, by the gamma-aminopropyl-triethoxy-silane of 44.0g (KH550) and 4.3g it is water-soluble in
4h is reacted in 40.0mL isopropanol and at 60 DEG C.After acquired solution is cooled to room temperature, alcoholic solvent is evaporated off, obtains colourless liquid,
That is the amino-containing hyperbranched polyorganosiloxane in end (HPSi).
2) preparation of sulfonyl glycine betaine methacrylate
At room temperature, 15.7g methacrylic acid 2- (dimethylamino) ethyl ester and 12.2g1,3- propane sultone are dissolved in
100mL chloroform and 100mL1 in 2- dichloroethanes are after mixing evenly warming up to 60 DEG C the reaction was continued 3h.Gained mixed liquor
It is filtered after being cooled to room temperature, obtains white powder, i.e. sulfonyl glycine betaine methacrylate.
3) preparation of linear propylene's acid resin of the glycine betaine containing sulfonyl
Under nitrogen protection, by 2.5g methyl methacrylate, 4.5g butyl acrylate, 2.0g sulfonyl glycine betaine methyl
Acrylate, 1.0g acetoacetate methacrylic acid glycol ester and 0.3g azodiisobutyronitrile are dissolved in 10mL ethyl alcohol and 10mL is different
In propyl alcohol, and it polymerize 2h at 70 DEG C.Gained mixed liquor is added in 50mL n-hexane, agitation and filtration, after filter cake ethanol washing
Vacuum drying, obtained solid are linear propylene's acid resin of the glycine betaine containing sulfonyl.
4) preparation of reversible selfreparing antimicrobial acrylic coating
The HPSi of linear propylene's acid resin of 6g glycine betaine containing sulfonyl and 0.4g is dissolved in 20mL methanol at 50 DEG C, is mixed
It closes uniformly, obtains colourless transparent solution；
Obtained solution is coated on glass surface, levelling obtains reversible selfreparing antimicrobial acrylic coating after dry.
5) self-repair method of reversible selfreparing antimicrobial acrylic coating
By damaged coating, selfreparing is handled 20 hours under conditions of temperature is 100 DEG C.
Embodiment 11
1) preparation of the amino-containing hyperbranched polyorganosiloxane in end (being denoted as HPSi)
Under nitrogen protection, by the gamma-aminopropyl-triethoxy-silane of 44.0g (KH550) and 4.3g it is water-soluble in
4h is reacted in 20.0mL methanol and 20.0mL ethyl alcohol and at 60 DEG C.After acquired solution is cooled to room temperature, alcoholic solvent is evaporated off, obtains
The amino-containing hyperbranched polyorganosiloxane of colourless liquid, i.e. end (HPSi).
2) preparation of sulfonyl glycine betaine methacrylate
At room temperature, 15.7g methacrylic acid 2- (dimethylamino) ethyl ester and 12.2g1,3- propane sultone are dissolved in
In 100mL1,2- dichloroethanes after mixing evenly, 65 DEG C are warming up to the reaction was continued 3h.Mistake after gained mixed liquor is cooled to room temperature
Filter, obtains white powder, i.e. sulfonyl glycine betaine methacrylate.
3) preparation of linear propylene's acid resin of the glycine betaine containing sulfonyl
Under nitrogen protection, by 2.5g methyl methacrylate, 4.5g butyl acrylate, 2.0g sulfonyl glycine betaine methyl
Acrylate, 1.0g acetoacetate methacrylic acid glycol ester and 0.3g azodiisobutyronitrile are being dissolved in 15mL ethyl alcohol and 15mL just
In butanol, and it polymerize 2h at 70 DEG C.Gained mixed liquor is added in 50mL n-hexane, agitation and filtration, after filter cake ethanol washing
Vacuum drying, obtained solid are linear propylene's acid resin of the glycine betaine containing sulfonyl.
4) preparation of reversible selfreparing antimicrobial acrylic coating
The HPSi of linear propylene's acid resin of 6g glycine betaine containing sulfonyl and 0.4g is dissolved in 20mL normal propyl alcohol at 50 DEG C,
It is uniformly mixed, obtains colourless transparent solution；
Obtained solution is coated on ptfe surface, levelling obtains reversible selfreparing antibacterial propylene after dry
It is acid coated.
5) self-repair method of reversible selfreparing antimicrobial acrylic coating
Using the self-repair method of embodiment 1.
Embodiment 12
1) preparation of the amino-containing hyperbranched polyorganosiloxane in end (being denoted as HPSi)
Under nitrogen protection, by the gamma-aminopropyl-triethoxy-silane of 44.0g (KH550) and 4.3g it is water-soluble in
4h is reacted in 30.0mL methanol and 30.0mL isopropanol and at 60 DEG C.After acquired solution is cooled to room temperature, alcoholic solvent is evaporated off, obtains
To colourless liquid, the i.e. amino-containing hyperbranched polyorganosiloxane in end (HPSi).
2) preparation of sulfonyl glycine betaine methacrylate
At room temperature, 15.7g methacrylic acid 2- (dimethylamino) ethyl ester and 12.2g1,3- propane sultone are dissolved in
In 100mL1,2- dichloroethanes after mixing evenly, 70 DEG C are warming up to the reaction was continued 3h.Mistake after gained mixed liquor is cooled to room temperature
Filter, obtains white powder, i.e. sulfonyl glycine betaine methacrylate.
3) preparation of linear propylene's acid resin of the glycine betaine containing sulfonyl
Under nitrogen protection, by 2.5g methyl methacrylate, 4.5g butyl acrylate, 2.0g sulfonyl glycine betaine methyl
Acrylate, 1.0g acetoacetate methacrylic acid glycol ester and 0.3g azodiisobutyronitrile are dissolved in 20mL ethyl alcohol, and
It polymerize 2h at 60 DEG C.Gained mixed liquor is added in 50mL n-hexane, agitation and filtration, is dried in vacuo after filter cake ethanol washing, institute
Obtain linear propylene's acid resin that solid is the glycine betaine containing sulfonyl.
4) preparation of reversible selfreparing antimicrobial acrylic coating
The HPSi of linear propylene's acid resin of 6g glycine betaine containing sulfonyl and 0.4g is dissolved in 20mL isopropanol at 50 DEG C,
It is uniformly mixed, obtains colourless transparent solution；
Obtained solution is coated on ptfe surface, levelling obtains reversible selfreparing antibacterial propylene after dry
It is acid coated.
5) self-repair method of reversible selfreparing antimicrobial acrylic coating
By damaged coating, selfreparing is handled 20 hours under conditions of temperature is 120 DEG C.
Embodiment 13
1) preparation of the amino-containing hyperbranched polyorganosiloxane in end (being denoted as HPSi)
Under nitrogen protection, by the gamma-aminopropyl-triethoxy-silane of 44.0g (KH550) and 4.3g it is water-soluble in
4h is reacted in 40.0mL ethyl alcohol and 40.0mL n-butanol and at 60 DEG C.After acquired solution is cooled to room temperature, alcoholic solvent is evaporated off, obtains
To colourless liquid, the i.e. amino-containing hyperbranched polyorganosiloxane in end (HPSi).
2) preparation of sulfonyl glycine betaine methacrylate
At room temperature, 15.7g methacrylic acid 2- (dimethylamino) ethyl ester and 12.2g1,3- propane sultone are dissolved in
In 100mL1,2- dichloroethanes after mixing evenly, 80 DEG C are warming up to the reaction was continued 3h.Mistake after gained mixed liquor is cooled to room temperature
Filter, obtains white powder, i.e. sulfonyl glycine betaine methacrylate.
3) preparation of linear propylene's acid resin of the glycine betaine containing sulfonyl
Under nitrogen protection, by 2.5g methyl methacrylate, 4.5g butyl acrylate, 2.0g sulfonyl glycine betaine methyl
Acrylate, 1.0g acetoacetate methacrylic acid glycol ester and 0.3g azodiisobutyronitrile are dissolved in 20mL ethyl alcohol, and
It polymerize 2h at 80 DEG C.Gained mixed liquor is added in 50mL n-hexane, agitation and filtration, is dried in vacuo after filter cake ethanol washing, institute
Obtain linear propylene's acid resin that solid is the glycine betaine containing sulfonyl.
4) preparation of reversible selfreparing antimicrobial acrylic coating
The HPSi of linear propylene's acid resin of 6g glycine betaine containing sulfonyl and 0.4g is dissolved in 20mL n-butanol at 50 DEG C,
It is uniformly mixed, obtains colourless transparent solution；
Obtained solution is coated on glass surface, levelling obtains reversible selfreparing antimicrobial acrylic coating after dry.
5) self-repair method of reversible selfreparing antimicrobial acrylic coating
Using the self-repair method of embodiment 1.
Embodiment 14
1) preparation of the amino-containing hyperbranched polyorganosiloxane in end (being denoted as HPSi)
Under nitrogen protection, by the gamma-aminopropyl-triethoxy-silane of 44.0g (KH550) and 4.3g it is water-soluble in
4h is reacted in 40.0mL ethyl alcohol and at 70 DEG C.After acquired solution is cooled to room temperature, alcoholic solvent is evaporated off, obtains colourless liquid, i.e.,
The amino-containing hyperbranched polyorganosiloxane in end (HPSi).
2) preparation of sulfonyl glycine betaine methacrylate
At room temperature, 15.7g methacrylic acid 2- (dimethylamino) ethyl ester and 12.2g1,3- propane sultone are dissolved in
In 100mL1,2- dichloroethanes after mixing evenly, 60 DEG C are warming up to the reaction was continued 4h.Mistake after gained mixed liquor is cooled to room temperature
Filter, obtains white powder, i.e. sulfonyl glycine betaine methacrylate.
3) preparation of linear propylene's acid resin of the glycine betaine containing sulfonyl
Under nitrogen protection, by 2.5g methyl methacrylate, 4.5g butyl acrylate, 2.0g sulfonyl glycine betaine methyl
Acrylate, 1.0g acetoacetate methacrylic acid glycol ester and 0.3g azodiisobutyronitrile are dissolved in 20mL ethyl alcohol, and
Polyase 13 h at 70 DEG C.Gained mixed liquor is added in 50mL n-hexane, agitation and filtration, is dried in vacuo after filter cake ethanol washing, institute
Obtain linear propylene's acid resin that solid is the glycine betaine containing sulfonyl.
4) preparation of reversible selfreparing antimicrobial acrylic coating
The HPSi of linear propylene's acid resin of 6g glycine betaine containing sulfonyl and 0.4g is dissolved in 20mL isobutanol at 50 DEG C,
It is uniformly mixed, obtains colourless transparent solution；
Obtained solution is coated on ptfe surface, levelling obtains reversible selfreparing antibacterial propylene after dry
It is acid coated.
5) self-repair method of reversible selfreparing antimicrobial acrylic coating
Using the self-repair method of embodiment 1.
Embodiment 15
1) preparation of the amino-containing hyperbranched polyorganosiloxane in end (being denoted as HPSi)
Under nitrogen protection, by the gamma-aminopropyl-triethoxy-silane of 44.0g (KH550) and 4.3g it is water-soluble in
4h is reacted in 40.0mL ethyl alcohol and at 80 DEG C.After acquired solution is cooled to room temperature, alcoholic solvent is evaporated off, obtains colourless liquid, i.e.,
The amino-containing hyperbranched polyorganosiloxane in end (HPSi).
2) preparation of sulfonyl glycine betaine methacrylate
At room temperature, 15.7g methacrylic acid 2- (dimethylamino) ethyl ester and 12.2g1,3- propane sultone are dissolved in
In 100mL1,2- dichloroethanes after mixing evenly, 60 DEG C are warming up to the reaction was continued 5h.Mistake after gained mixed liquor is cooled to room temperature
Filter, obtains white powder, i.e. sulfonyl glycine betaine methacrylate.
3) preparation of linear propylene's acid resin of the glycine betaine containing sulfonyl
Under nitrogen protection, by 2.5g methyl methacrylate, 4.5g butyl acrylate, 2.0g sulfonyl glycine betaine methyl
Acrylate, 1.0g acetoacetate methacrylic acid glycol ester and 0.3g azodiisobutyronitrile are dissolved in 20mL ethyl alcohol, and
It polymerize 4h at 70 DEG C.Gained mixed liquor is added in 50mL n-hexane, agitation and filtration, is dried in vacuo after filter cake ethanol washing, institute
Obtain linear propylene's acid resin that solid is the glycine betaine containing sulfonyl.
4) preparation of reversible selfreparing antimicrobial acrylic coating
At 50 DEG C by the HPSi of linear propylene's acid resin of 6g glycine betaine containing sulfonyl and 0.4g be dissolved in 10mL methanol and
In 10mL ethyl alcohol, it is uniformly mixed and obtains colourless transparent solution；
Obtained solution is coated on glass surface, levelling obtains reversible selfreparing antimicrobial acrylic coating after dry.
5) self-repair method of reversible selfreparing antimicrobial acrylic coating
By damaged coating, selfreparing is handled 10 hours under conditions of temperature is 110 DEG C.
Embodiment 16
1) preparation of the amino-containing hyperbranched polyorganosiloxane in end (being denoted as HPSi)
Under nitrogen protection, by the gamma-aminopropyl-triethoxy-silane of 44.0g (KH550) and 4.3g it is water-soluble in
5h is reacted in 40.0mL ethyl alcohol and at 60 DEG C.After acquired solution is cooled to room temperature, alcoholic solvent is evaporated off, obtains colourless liquid, i.e.,
The amino-containing hyperbranched polyorganosiloxane in end (HPSi).
2) preparation of sulfonyl glycine betaine methacrylate
At room temperature, 15.7g methacrylic acid 2- (dimethylamino) ethyl ester and 12.2g1,3- propane sultone are dissolved in
In 100mL1,2- dichloroethanes after mixing evenly, 60 DEG C are warming up to the reaction was continued 5.5h.Mistake after gained mixed liquor is cooled to room temperature
Filter, obtains white powder, i.e. sulfonyl glycine betaine methacrylate.
3) preparation of linear propylene's acid resin of the glycine betaine containing sulfonyl
Under nitrogen protection, by 2.5g methyl methacrylate, 4.5g butyl acrylate, 2.0g sulfonyl glycine betaine methyl
Acrylate, 1.0g acetoacetate methacrylic acid glycol ester and 0.3g azodiisobutyronitrile are dissolved in 20mL ethyl alcohol, and
It polymerize 2h at 70 DEG C.Gained mixed liquor is added in 55mL n-hexane, agitation and filtration, is dried in vacuo after filter cake ethanol washing, institute
Obtain linear propylene's acid resin that solid is the glycine betaine containing sulfonyl.
4) preparation of reversible selfreparing antimicrobial acrylic coating
At 50 DEG C by the HPSi of linear propylene's acid resin of 6g glycine betaine containing sulfonyl and 0.4g be dissolved in 15mL ethyl alcohol and
In 15mL n-butanol, it is uniformly mixed, obtains colourless transparent solution；
Obtained solution is coated on ptfe surface, levelling obtains reversible selfreparing antibacterial propylene after dry
It is acid coated.
5) self-repair method of reversible selfreparing antimicrobial acrylic coating
By damaged coating, selfreparing is handled 18 hours under conditions of temperature is 110 DEG C.
Embodiment 17
1) preparation of the amino-containing hyperbranched polyorganosiloxane in end (being denoted as HPSi)
Under nitrogen protection, by the gamma-aminopropyl-triethoxy-silane of 44.0g (KH550) and 4.3g it is water-soluble in
6h is reacted in 40.0mL ethyl alcohol and at 60 DEG C.After acquired solution is cooled to room temperature, alcoholic solvent is evaporated off, obtains colourless liquid, i.e.,
The amino-containing hyperbranched polyorganosiloxane in end (HPSi).
2) preparation of sulfonyl glycine betaine methacrylate
At room temperature, 15.7g methacrylic acid 2- (dimethylamino) ethyl ester and 12.2g1,3- propane sultone are dissolved in
In 100mL1,2- dichloroethanes after mixing evenly, 60 DEG C are warming up to the reaction was continued 6h.Mistake after gained mixed liquor is cooled to room temperature
Filter, obtains white powder, i.e. sulfonyl glycine betaine methacrylate.
3) preparation of linear propylene's acid resin of the glycine betaine containing sulfonyl
Under nitrogen protection, by 2.5g methyl methacrylate, 4.5g butyl acrylate, 2.0g sulfonyl glycine betaine methyl
Acrylate, 1.0g acetoacetate methacrylic acid glycol ester and 0.3g azodiisobutyronitrile are dissolved in 20mL ethyl alcohol, and
It polymerize 2h at 70 DEG C.Gained mixed liquor is added in 60mL n-hexane, agitation and filtration, is dried in vacuo after filter cake ethanol washing, institute
Obtain linear propylene's acid resin that solid is the glycine betaine containing sulfonyl.
4) preparation of reversible selfreparing antimicrobial acrylic coating
The HPSi of linear propylene's acid resin of 6g glycine betaine containing sulfonyl and 0.4g is dissolved in 15mL isopropanol at 50 DEG C
In 15mL n-butanol, it is uniformly mixed, obtains colourless transparent solution；
Obtained solution is coated on ptfe surface, levelling obtains reversible selfreparing antibacterial propylene after dry
It is acid coated.
5) self-repair method of reversible selfreparing antimicrobial acrylic coating
By damaged coating, selfreparing is handled 12 hours under conditions of temperature is 120 DEG C.
Claims (8)
1. a kind of preparation method of reversible selfreparing antimicrobial acrylic coating, it is characterised in that include the following steps:
(1) under inert gas protection, by mass, by 10 parts of gamma-aminopropyl-triethoxy-silanes, 1~1.5 part it is water-soluble in 10
In~20 parts of alcoholic solvents, it is uniformly mixed；4~6h is reacted under conditions of inert gas shielding, temperature are 60~80 DEG C, gained is molten
After liquid is cooled to room temperature, alcoholic solvent is evaporated off, obtained colourless liquid is amino-containing hyperbranched polyorganosiloxane；
(2) at room temperature, 16 parts of methacrylic acid -2- (dimethylamino) ethyl esters and 12~15 parts of 1,3-propane sultone are dissolved in
In 100~200 parts of alkyl chlorides, after mixing evenly, 60~80 DEG C are warming up to the reaction was continued 3~6h, gained mixed liquor is cooled to room
It is filtered after temperature, obtained white powder is sulfonyl glycine betaine methacrylate；
(3) under inert gas protection, by 2.5 parts of methyl methacrylates, 4.5 parts of butyl acrylates, 2 portions of sulfonyl beets
Alkali methacrylate, 1 part of acetoacetate methacrylic acid glycol ester and 0.3 part of azodiisobutyronitrile are dissolved in 20~30 parts of alcohol
In solvent, 2~4h is polymerize under conditions of temperature is 60~80 DEG C, obtains mixed liquor；Mixed liquor is being added to 50~60 parts just
In hexane, agitation and filtration, filter cake is dried in vacuo after being washed with alcoholic solvent, and obtained solid is linear third of the glycine betaine containing sulfonyl
Olefin(e) acid resin；
(4) under conditions of temperature is 50~60 DEG C, the linear propylene's acid for the glycine betaine containing sulfonyl that 6 parts of steps (3) are obtained
The amino-containing hyperbranched polyorganosiloxane that resin and 0.2~0.6 part of step (1) obtain is dissolved in 20~30 parts of alcoholic solvents, is mixed
It closes uniformly, obtains colourless transparent solution；
(5) solution for obtaining step (4) is coated on substrate surface, obtains a kind of reversible selfreparing antimicrobial acrylic after dry
Coating.
2. a kind of preparation method of reversible selfreparing antimicrobial acrylic coating according to claim 1, it is characterised in that: institute
The inert gas stated is one kind or their any combination of nitrogen, argon gas.
3. a kind of preparation method of reversible selfreparing antimicrobial acrylic coating according to claim 1, it is characterised in that: institute
The alcoholic solvent stated is one of methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, isobutanol or their any combination.
4. a kind of preparation method of reversible selfreparing antimicrobial acrylic coating according to claim 1, it is characterised in that: institute
The alkyl chloride stated is one of methylene chloride, chloroform, 1,2- dichloroethanes or their any combination.
5. a kind of preparation method of reversible selfreparing antimicrobial acrylic coating according to claim 1, it is characterised in that: institute
The substrate stated is metal material, inorganic non-metallic material or organic material.
6. a kind of preparation method of reversible selfreparing antimicrobial acrylic coating according to claim 5, it is characterised in that: institute
The metal material stated is aluminium alloy plate；The inorganic non-metallic material is glass；The organic material is polytetrafluoroethylene (PTFE).
7. a kind of reversible selfreparing antimicrobial acrylic coating obtained by claim 1 preparation method.
8. a kind of self-repair method of reversible selfreparing antimicrobial acrylic coating as claimed in claim 7, damaged coating is existed
Selfreparing is handled 8~24 hours under conditions of temperature is 60~120 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710230353.4A CN106928797B (en) | 2017-04-10 | 2017-04-10 | A kind of reversible selfreparing antimicrobial acrylic coating, preparation and self-repair method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710230353.4A CN106928797B (en) | 2017-04-10 | 2017-04-10 | A kind of reversible selfreparing antimicrobial acrylic coating, preparation and self-repair method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106928797A CN106928797A (en) | 2017-07-07 |
| CN106928797B true CN106928797B (en) | 2019-02-19 |
Family
ID=59426436
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710230353.4A Active CN106928797B (en) | 2017-04-10 | 2017-04-10 | A kind of reversible selfreparing antimicrobial acrylic coating, preparation and self-repair method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106928797B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108948250B (en) * | 2018-06-14 | 2021-08-31 | 广州大学 | Antibacterial polymer emulsion and preparation method and application thereof |
| CN110684220B (en) * | 2018-06-22 | 2022-04-15 | 苏州大学 | Transparent foldable polysiloxane membrane that curls |
| US11479671B2 (en) | 2018-07-04 | 2022-10-25 | Soochow University | Transparent rollable folded polysiloxane film and preparation and self-repairing method thereof |
| CN112745731B (en) * | 2021-01-19 | 2021-11-26 | 江西星高新材料有限公司 | Hyperbranched polymer-containing waterborne antifouling composite coating and preparation method thereof |
| CN115785806B (en) * | 2022-11-04 | 2023-08-04 | 鼎钰玻璃(扬州)有限公司 | Photovoltaic glass coated with organic-inorganic hybrid coating and processing technology thereof |
| CN116515121B (en) * | 2023-04-28 | 2023-10-31 | 广州腾富新材料科技有限公司 | High-solid low-viscosity acrylic resin and application thereof in automotive interior coating |
| CN117343372B (en) * | 2023-10-27 | 2024-02-20 | 无锡德泰纳维高新材料有限公司 | Antibacterial plastic and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007082153A2 (en) * | 2006-01-05 | 2007-07-19 | The Board Of Trustees Of The University Of Illinois | Self-healing coating system |
| CN105176063A (en) * | 2015-08-02 | 2015-12-23 | 苏州大学 | Thermal-reversible self-repair polyurethane membrane and preparation method therefor |
| CN105400405A (en) * | 2015-10-30 | 2016-03-16 | 华南理工大学 | Self-repairing organic silicon polyurethane/polyurea anti-pollution material as well as method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MY163472A (en) * | 2012-07-24 | 2017-09-15 | Petroliam Nasional Berhad (Petronas) | Polymer compositions |
-
2017
- 2017-04-10 CN CN201710230353.4A patent/CN106928797B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007082153A2 (en) * | 2006-01-05 | 2007-07-19 | The Board Of Trustees Of The University Of Illinois | Self-healing coating system |
| CN105176063A (en) * | 2015-08-02 | 2015-12-23 | 苏州大学 | Thermal-reversible self-repair polyurethane membrane and preparation method therefor |
| CN105400405A (en) * | 2015-10-30 | 2016-03-16 | 华南理工大学 | Self-repairing organic silicon polyurethane/polyurea anti-pollution material as well as method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| "Hyperbranched polymers from propargyloxysilanes:New types of acetylenic resins.";XiaoYX ect.;《Polymer Chemistry》;20011101;第39卷(第19期);第3383-3391页 * |
| "超支化聚硅氧烷合成与应用的研究进展";季立富等;《材料导报》;20090228(第3期);第35-38页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106928797A (en) | 2017-07-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106928797B (en) | A kind of reversible selfreparing antimicrobial acrylic coating, preparation and self-repair method | |
| CN102712700B (en) | There is the aquagel derivative as coating agent of broad spectrum antibiotic activity | |
| Kurowska et al. | A simultaneously antimicrobial, protein-repellent, and cell-compatible polyzwitterion network | |
| JP2015083699A (en) | Ship coating | |
| Song et al. | Bioinspired durable antibacterial and antifouling coatings based on borneol fluorinated polymers: demonstrating direct evidence of antiadhesion | |
| Shi et al. | Host–guest self-assembly toward reversible thermoresponsive switching for bacteria killing and detachment | |
| Aumsuwan et al. | Antibacterial surfaces on expanded polytetrafluoroethylene; penicillin attachment | |
| Lee et al. | Development of multimodal antibacterial surfaces using porous amine-reactive films incorporating lubricant and silver nanoparticles | |
| Yong et al. | Conformal hydrogel coatings on catheters to reduce biofouling | |
| US20170174907A1 (en) | Marine coatings | |
| Pan et al. | Degradable vinyl polymers for combating marine biofouling | |
| CN105294887A (en) | Amphion polymer modified anti-adhesion surface with dopamine as anchor, and making method thereof | |
| Chen et al. | Preparation and performance of amphiphilic polyurethane copolymers with capsaicin-mimic and peg moieties for protein resistance and antibacteria | |
| JP2007302651A (en) | Photocurable monomer including imidazolium salt, antimicrobial and photocurable composition containing the monomer, and antimicrobial polymeric material produced from the composition | |
| CN102079713A (en) | Cross-linked polyquaternary ammonium salt type antibiosis monomer, preparation method of cross-linked polyquaternary ammonium salt type antibiosis monomer and application of cross-linked polyquaternary ammonium salt type antibiosis monomer in dentistry repairing materials | |
| Ignatova et al. | Stainless steel grafting of hyperbranched polymer brushes with an antibacterial activity: synthesis, characterization, and properties | |
| CN104031236B (en) | With the urethane and its production and use of zwitter-ion precursor brush side chain | |
| CN110437727B (en) | N-hydroxyethyl acrylamide-based antibacterial/antifogging coating and preparation method thereof | |
| CN103524656A (en) | NT-BMPkE with bacteria resistance as well as preparation and application thereof | |
| RU2008135693A (en) | MONOMERS AND POLYMERS BASED ON 1,3 / 1,4-CYCLOHEXANDIMETHANOL | |
| Schneider-Chaabane et al. | Stimulus-responsive polyzwitterionic surfaces made from itaconic acid: self-triggered antimicrobial activity, protein repellency, and cell compatibility | |
| Shum et al. | UV-curable surface-attached antimicrobial polymeric onium coatings: designing effective, solvent-resistant coatings for plastic surfaces | |
| Faÿ et al. | Additives for efficient biodegradable antifouling paints | |
| Zhou et al. | Effect of metal ions with reducing properties on hydrogels containing catechol groups | |
| EP3510112A2 (en) | A simultaneously antimicrobial and protein-repellent polyzwitterion |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |