CN110437699B - Amphiphilic polymer antifogging antibacterial coating containing betaine zwitterion and preparation method thereof - Google Patents
Amphiphilic polymer antifogging antibacterial coating containing betaine zwitterion and preparation method thereof Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 86
- 239000011248 coating agent Substances 0.000 title claims abstract description 82
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 54
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229960003237 betaine Drugs 0.000 title claims abstract description 53
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 title claims abstract description 42
- 229920000642 polymer Polymers 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- -1 alkyl methacrylate Chemical compound 0.000 claims abstract description 32
- 229920001744 Polyaldehyde Polymers 0.000 claims abstract description 16
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 16
- 125000003118 aryl group Chemical group 0.000 claims abstract description 16
- 238000004132 cross linking Methods 0.000 claims abstract description 12
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- JWNWCEAWZGLYTE-UHFFFAOYSA-N 2-(trimethylazaniumyl)butanoate Chemical compound CCC(C([O-])=O)[N+](C)(C)C JWNWCEAWZGLYTE-UHFFFAOYSA-N 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 60
- 239000011521 glass Substances 0.000 claims description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 35
- 239000000758 substrate Substances 0.000 claims description 34
- 239000002904 solvent Substances 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical group CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- 238000009832 plasma treatment Methods 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- XSHISXQEKIKSGC-UHFFFAOYSA-N 2-aminoethyl 2-methylprop-2-enoate;hydron;chloride Chemical compound Cl.CC(=C)C(=O)OCCN XSHISXQEKIKSGC-UHFFFAOYSA-N 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- 238000003618 dip coating Methods 0.000 claims description 4
- 238000001548 drop coating Methods 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 238000004528 spin coating Methods 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 230000000845 anti-microbial effect Effects 0.000 claims 1
- 238000002715 modification method Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 abstract description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 2
- QLIBJPGWWSHWBF-UHFFFAOYSA-N 2-aminoethyl methacrylate Chemical compound CC(=C)C(=O)OCCN QLIBJPGWWSHWBF-UHFFFAOYSA-N 0.000 abstract 1
- VCGRAVNMFQKLPJ-UHFFFAOYSA-N Cl.C(C(=C)C)(=O)ON Chemical compound Cl.C(C(=C)C)(=O)ON VCGRAVNMFQKLPJ-UHFFFAOYSA-N 0.000 abstract 1
- 229940117986 sulfobetaine Drugs 0.000 description 14
- 239000003814 drug Substances 0.000 description 13
- 229940079593 drug Drugs 0.000 description 10
- 238000002834 transmittance Methods 0.000 description 10
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 description 9
- 230000001580 bacterial effect Effects 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 239000000178 monomer Substances 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 5
- IZALUMVGBVKPJD-UHFFFAOYSA-N benzene-1,3-dicarbaldehyde Chemical compound O=CC1=CC=CC(C=O)=C1 IZALUMVGBVKPJD-UHFFFAOYSA-N 0.000 description 5
- 229940054441 o-phthalaldehyde Drugs 0.000 description 5
- ZWLUXSQADUDCSB-UHFFFAOYSA-N phthalaldehyde Chemical group O=CC1=CC=CC=C1C=O ZWLUXSQADUDCSB-UHFFFAOYSA-N 0.000 description 5
- 241000894006 Bacteria Species 0.000 description 4
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 210000000170 cell membrane Anatomy 0.000 description 3
- 239000001963 growth medium Substances 0.000 description 3
- KSPSCTPWZXCFPO-UHFFFAOYSA-N 2-chloroethanamine 2-methylprop-2-enoic acid Chemical compound NCCCl.C(C(=C)C)(=O)O KSPSCTPWZXCFPO-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 230000003385 bacteriostatic effect Effects 0.000 description 2
- 238000010382 chemical cross-linking Methods 0.000 description 2
- 238000012258 culturing Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- 208000035143 Bacterial infection Diseases 0.000 description 1
- VTWOOHKJQIZXKD-UHFFFAOYSA-N C(C(=C)C)(=O)O.NCl Chemical compound C(C(=C)C)(=O)O.NCl VTWOOHKJQIZXKD-UHFFFAOYSA-N 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- AJXBTRZGLDTSST-UHFFFAOYSA-N amino 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)ON AJXBTRZGLDTSST-UHFFFAOYSA-N 0.000 description 1
- 208000022362 bacterial infectious disease Diseases 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 230000009036 growth inhibition Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- ZUHZZVMEUAUWHY-UHFFFAOYSA-N n,n-dimethylpropan-1-amine Chemical compound CCCN(C)C ZUHZZVMEUAUWHY-UHFFFAOYSA-N 0.000 description 1
- WXEFTOZJECWFCW-UHFFFAOYSA-N n,n-dimethylpropan-1-amine;2-methylprop-2-enoic acid Chemical compound CCCN(C)C.CC(=C)C(O)=O WXEFTOZJECWFCW-UHFFFAOYSA-N 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical group CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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- 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
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
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- 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
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- 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
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract
The invention discloses an amphiphilic polymer antifogging antibacterial coating containing betaine zwitterions and a preparation method thereof. The coating is prepared by the cross-linking reaction of poly (alkyl methacrylate-co-methacrylic acid-2-aminoethyl ester-co-methacryloyl ethyl betaine) prepared by free radical polymerization of alkyl methacrylate, amino methacrylate hydrochloride and betaine methacrylate and aromatic polyaldehyde. The betaine zwitterion has good antifogging and biocompatibility, the 2-aminoethyl methacrylate has a bactericidal effect, the alkyl methacrylate can endow the coating with good film forming property, and can improve the bactericidal capability of the coating by cooperating with the amino, and the aromatic polyaldehyde can perform a crosslinking reaction with partial amino to form a crosslinking network with a stable structure. The invention has the advantages of easily obtained raw materials, simple and convenient preparation, good antifogging property, antibacterial property, biocompatibility and structural stability, and wide application prospect.
Description
Technical Field
The invention relates to an amphiphilic polymer antifogging antibacterial coating containing betaine zwitterions and a preparation method thereof.
Background
Optical lenses are often used as important components in various types of precision equipment, such as sensors, laparoscopes, endoscopes, periscopes, and the like. Therefore, the lens is required to maintain good light transmittance for a long period of time. When the equipment works in specific complex environments such as human or animal bodies, pipelines, sea surfaces and the like, the equipment can not work normally due to fog generated on the lenses, a large amount of bacteria can be bred in a damp environment, and the bacteria can be attached to the lenses to further influence the normal use of the equipment and damage the lenses. Bacterial infections can also cause serious medical accidents, particularly in the field of medical devices. Therefore, in order to make such important equipment still operate normally and safely under complex environments, a protective coating layer with anti-fog and anti-bacterial functions is required to be coated on the surface of the lens.
At present, most of common antifogging coatings are hydrophilic materials or amphiphilic materials, and the antibacterial method comprises metal nanoparticle antibacterial, metal oxide antibacterial, cation antibacterial and the like. Ming et al synthesized an amphiphilic random copolymer of quaternary ammonium salt, mixed with ethylene glycol dimethacrylate, and crosslinked by UV curing to form an amphiphilic antifogging antibacterial coating with a semi-interpenetrating network structure (ZHao J, Ma L, Millians W, Wu T, Ming W.Dual-functional antibacterial/antibacterial polymer coating. ACS applied materials & interfaces,2016,8(13), 8737-8742). However, a large number of experiments show that the amphiphilic coating with the semi-interpenetrating network structure is difficult to maintain stability in water for a long time because chemical bonds are not connected among polymer chains, and the coating can swell and dissolve in a short time. Therefore, an antifogging and antibacterial coating with a more stable structure is urgently needed.
Disclosure of Invention
According to the invention, alkyl methacrylate monomers, amino methacrylate monomers and betaine methacrylate monomers are subjected to free radical polymerization to obtain a polymer poly (alkyl methacrylate-co-methacrylic acid-2-aminoethyl ester-co-methacryloyl ethyl betaine), and aromatic polyaldehyde is introduced as a cross-linking agent to form an amphiphilic polymer chemical cross-linking network, so that the transparent coating material which has good antifogging and antibacterial properties and has water stability and biocompatibility is prepared. The material has a chemical crosslinking network, so that the structure is more stable compared with a conventional physical crosslinking structure and a semi-interpenetrating network structure, and the prepared coating can stably exist in water for a long time. The alkyl methacrylate monomer has hydrophobicity, and can improve the stability of the coating. The introduction of the methacrylic acid amino hydrochloride monomer can not only provide a crosslinking site, but also enable the coating to have antibacterial property. Because the methacrylic betaine monomer has good hydrophilicity, the coating can have antifogging property.
The amphiphilic polymer coating prepared by the invention has excellent antifogging property, antibacterial property and stability, can be applied to various complex environments, overcomes the limitation of a coating material with a single function on application, has practical application value, is easy to obtain raw materials, is simple and convenient in preparation method, and has few reports on related contents so far.
The invention discloses an amphiphilic polymer antifogging antibacterial coating containing betaine zwitter-ions, which is characterized by comprising the following components in percentage by mass:
poly (alkyl methacrylate-co-2-aminoethyl methacrylate-co-methacryloylethyl betaine): 2-70%;
aromatic polyaldehydes: 0.5-20%;
solvent: and (4) the balance.
Wherein, the methacrylethyl betaine is methacrylethyl sulfobetaine or methacrylethyl carboxybetaine, and the aromatic polyaldehyde is o-phthalaldehyde or m-phthalaldehyde or trimeldehyde.
The structural formula of the poly (alkyl methacrylate-co-2-aminoethyl methacrylate-co-methacryloylethylbetaine) is as follows:
wherein a is 10-20, b is 40-80, c is 10-40, and n is 0-17. a, b, c and n are integers.
R is
The structural formula of the aromatic polyaldehyde is as follows:
the synthesis method of the poly (alkyl methacrylate-co-methacrylic acid-2-aminoethyl ester-co-methacryloyl ethyl betaine) comprises the following steps:
weighing the above substances as solutes according to a molar ratio of (10-20) to (40-80) of alkyl methacrylate, methacrylic acid-2-aminoethyl ester hydrochloride and methacryloyl ethyl betaine (10-40), dissolving the substances as the solutes in trifluoroethanol as a solvent to prepare a solution with a solute mass fraction of 10-40%, adding an initiator azobisisobutyronitrile with a mass equal to 1% of the solute mass, placing the solution in a Schlenk bottle for reaction, performing freeze-thaw cycling for three times, heating the solution in an oil bath at 60-80 ℃ for 10-12 hours for free radical polymerization, adding a small amount of sodium hydroxide until the pH of the solution is 9 after the reaction is finished, and dialyzing the solution in deionized water for three days.
The preparation method of the amphiphilic polymer antifogging and antibacterial coating containing the betaine zwitterion comprises the following steps:
preparing a solution from poly (alkyl methacrylate-co-methacrylic acid-2-aminoethyl ester-co-methacryloyl ethyl betaine), aromatic polyaldehyde and a solvent according to the mass percentage, coating the solution on the surface of a modified glass substrate, drying the surface at the temperature of 20-50 ℃ for 1-5 hours to remove the solvent, transferring the surface to the temperature of 70-100 ℃ and heating the surface for 5-10 hours to perform crosslinking, thus obtaining the antifogging antibacterial coating.
The method for modifying the surface of the base material comprises the following steps: and carrying out plasma treatment on the glass sheet, then soaking the glass sheet in a 1-20% methanol solution of a silane coupling agent for 2-10 h, finally respectively carrying out ultrasonic treatment on the glass sheet for 5min by using methanol and ethanol, and drying the glass sheet at room temperature.
The silane coupling agent is (3-aminopropyl) trimethoxy silane.
The coating method may employ drop coating, spray coating, spin coating, dip coating, and the like.
The solvent used in the preparation method of the betaine zwitterionic polymer antifogging coating is one or a mixed solvent of trifluoroethanol, methanol, tetrahydrofuran and ethanol.
The antifogging test and the antibacterial test are as follows:
antifogging test: and (3) placing the transparent base material with the coatings coated on the two sides in an environment at the temperature of-20 ℃ for 2 hours, then transferring the transparent base material to a room temperature environment to rapidly observe the change of the surface transparency, and measuring the light transmittance value of the transparent base material at the waveband of 400-800 nm. The result shows that compared with the prior invention, the coating still can keep good transparency after being placed for a longer time in a low-temperature environment, the light transmittance of the coating can reach 90.2 percent when being measured, and the light transmittance is equal to or slightly higher than that of a glass sheet which is not coated with the coating, so that the coating has more outstanding antifogging performance.
And (3) antibacterial testing: and (2) sterilizing the glass substrate coated with the single-side coating, respectively placing the glass substrate into a culture medium solution of staphylococcus aureus and escherichia coli, culturing for 24 hours at 37 ℃, taking a certain amount of cultured bacterial liquid, diluting, dropwise adding the diluted bacterial liquid onto a solid culture medium, culturing for 18 hours at 37 ℃, taking out, counting the number of bacterial colonies on the solid culture medium, and calculating the bacteriostasis rate. The calculation result shows that the coating has the antibacterial rate as high as 99.7 percent and has excellent antibacterial performance.
The invention takes methacrylic acid alkyl ester, methacrylic acid-2-amino ethyl ester hydrochloride and methacryl ethyl sulfobetaine or methacryl ethyl carboxyl betaine as main raw materials, obtains an amphiphilic random copolymer through free radical polymerization reaction, and is added with trimesic aldehyde for thermal crosslinking to form a film. Wherein, the betaine has good hydration capability, so that the coating has antifogging property and biocompatibility; the primary amine cation can adsorb a bacterial cell membrane with negative electricity, and is combined with the bacterial cell membrane to destroy the structure of the bacterial cell membrane, so that the bactericidal effect is achieved; the alkyl methacrylate has hydrophobicity, can obviously improve the stability of the coating and endows the polymer with good film forming property.
The invention is characterized in that the coating has antifogging and antibacterial functions under the condition of not influencing the transparency and thickness of the coating, has biocompatibility, can stably exist in water for a long time, and overcomes the problem that the prior coating has single function and is difficult to apply in a complex environment. In addition, the antibacterial material often kills cells of living bodies together, and the hydrophilic and amphiphilic antifogging coating often has difficulty in stably existing in water. Such problems are all solved in the present invention.
Drawings
FIG. 1: bacterial growth inhibition of the coating (left) and the plain glass slide (right).
Detailed Description
The technical solution of the present invention is further explained below with reference to the embodiments.
Example 1
The amphiphilic polymer antifogging antibacterial coating containing betaine zwitterions comprises the following components in percentage by mass:
poly (alkyl methacrylate-co-2-aminoethyl methacrylate-co-methacryloylethyl betaine): 2 percent;
aromatic polyaldehydes: 2 percent;
solvent: 96 percent.
(1) Preparation of poly (methyl methacrylate-co-2-aminoethyl methacrylate-co-methacryloylethyl carboxybetaine):
weighing medicines serving as solutes and dissolving the medicines in a molar ratio of 10:80:10, namely methyl methacrylate, methacrylic acid-2-aminoethyl ester hydrochloride and methacrylic acid dimethyl propyl aminoethyl carboxylate, dissolving the medicines in a trifluoroethanol solvent to prepare a solution with the mass fraction of the solutes of 10%, and adding an initiator azodiisobutyronitrile with the mass equal to 1% of the mass of the solutes. Sealing the reactants in a Schlenk bottle, performing freeze-thaw cycle for three times, heating in an oil bath at 60 ℃ for 10 hours to perform free radical polymerization to obtain poly (methyl methacrylate-co-methacrylic acid-2-aminoethyl ester-co-methacryloyl ethyl carboxyl betaine), wherein the structural formula of the poly (methyl methacrylate-co-methacrylic acid-2-aminoethyl ester-co-methacryloyl ethyl carboxyl betaine) is as follows:
(2) preparing the stable betaine amphiphilic polymer antifogging antibacterial coating:
and (3) carrying out plasma treatment on the glass sheet, soaking the glass sheet in a methanol solution of 1% of (3-aminopropyl) trimethoxy silane for 2 hours, respectively carrying out ultrasonic treatment on the glass sheet for 5min by using methanol and ethanol, and drying to obtain the glass substrate with the aminated surface. Preparing solution from poly (methyl methacrylate-co-methacrylic acid-2-aminoethyl ester-co-methacryloylethyl carboxyl betaine), o-phthalaldehyde and methanol according to the mass ratio of 2:2:96, coating the solution on the treated substrate by adopting a spin coating method, standing the substrate in an environment at 20 ℃ for 1 hour to slowly volatilize the solvent, transferring the substrate to an environment at 70 ℃ and heating the substrate for 2 hours to form a film by crosslinking, thus obtaining the betaine type amphiphilic polymer antifogging and antibacterial coating with stable structure.
The structural formula of the o-phthalaldehyde is as follows:
experiments show that the coating has good antifogging property and the light transmittance is 90.2%. The bacteriostatic rate of the coating is 99.2%.
Example 2
The amphiphilic polymer antifogging antibacterial coating containing betaine zwitterions comprises the following components in percentage by mass:
poly (alkyl methacrylate-co-2-aminoethyl methacrylate-co-methacryloylethyl betaine): 20 percent;
aromatic polyaldehydes: 20 percent;
solvent: 60 percent.
(1) Preparation of poly (propyl methacrylate-co-2-aminoethyl methacrylate-co-methacryloylethyl carboxybetaine):
weighing a medicine serving as a solute and dissolving the medicine into a trifluoroethanol solvent according to the mol ratio of 15:60:25, wherein the medicine is propyl methacrylate, methacrylic acid-2-aminoethyl ester hydrochloride and methacrylic acid dimethyl propyl aminoethyl carboxylate, preparing a solution with the mass fraction of the solute of 10%, and adding an initiator azodiisobutyronitrile with the mass equal to 1% of the mass of the solute. Sealing the reactants in a Schlenk bottle, performing freeze-thaw cycle for three times, and heating in an oil bath at 60 ℃ for 10 hours to perform free radical polymerization to obtain poly (propyl methacrylate-co-2-aminoethyl methacrylate-co-methacryloyl ethyl carboxyl betaine), wherein the structural formula of the poly (propyl methacrylate-co-2-aminoethyl methacrylate-co-methacryloyl ethyl carboxyl betaine) is as follows:
(2) preparing the stable betaine amphiphilic polymer antifogging antibacterial coating:
and (3) carrying out plasma treatment on the glass sheet, soaking the glass sheet in a methanol solution of 5 percent (3-aminopropyl) trimethoxy silane for 5 hours, respectively carrying out ultrasonic treatment on the glass sheet for 5min by using methanol and ethanol, and drying to obtain the glass substrate with the aminated surface. Preparing solution from poly (propyl methacrylate-co-methacrylic acid-2-aminoethyl ester-co-methacryloylethyl carboxyl betaine), m-phthalaldehyde and ethanol according to the mass ratio of 20:20:60, coating the solution on the treated substrate by adopting a dip coating method, standing the substrate in an environment at 30 ℃ for 2 hours to slowly volatilize the solvent, transferring the substrate to an environment at 80 ℃ and heating the substrate for 5 hours to form a film by crosslinking, thus obtaining the betaine type amphiphilic polymer antifogging and antibacterial coating with stable structure.
The structural formula of the isophthalaldehyde used is as follows:
experiments show that the coating has good antifogging property and the light transmittance is 90.0%. The coating bacteriostasis rate is 98.9%.
Example 3
The amphiphilic polymer antifogging antibacterial coating containing betaine zwitterions comprises the following components in percentage by mass:
poly (alkyl methacrylate-co-2-aminoethyl methacrylate-co-methacryloylethyl betaine): 35 percent;
aromatic polyaldehydes: 10 percent;
solvent: and 55 percent.
(1) Preparation of poly (n-butyl methacrylate-co-2-aminoethyl methacrylate-co-methacryloylethyl sulfobetaine):
weighing medicines serving as solutes and dissolving the medicines in a trifluoroethanol solvent according to a molar ratio of 20:50:30, namely n-butyl methacrylate, methacrylic acid-2-aminoethyl hydrochloride and methacrylic acid dimethyl propyl amine ethyl sulfonate to prepare a solution with the mass fraction of the solutes of 20%, and adding an initiator azodiisobutyronitrile with the mass equal to 1% of the mass of the solutes. Sealing the reactants in a Schlenk bottle, performing freeze-thaw cycle for three times, and heating in an oil bath at 65 ℃ for 10 hours to perform free radical polymerization to obtain poly (n-butyl methacrylate-co-2-aminoethyl methacrylate-co-methacryloylethyl sulfobetaine), wherein the structural formula of the poly (n-butyl methacrylate-co-2-aminoethyl methacrylate-co-methacryloylethyl sulfobetaine) is as follows:
(2) preparing the stable betaine amphiphilic polymer antifogging antibacterial coating:
and (3) carrying out plasma treatment on the glass sheet, soaking the glass sheet in a methanol solution of 10 percent (3-aminopropyl) trimethoxy silane for 8 hours, respectively carrying out ultrasonic treatment on the glass sheet for 5min by using methanol and ethanol, and drying to obtain the glass substrate with the aminated surface. Preparing solution from poly (n-butyl methacrylate-co-methacrylic acid-2-aminoethyl ester-co-methacryloyl ethyl sulfobetaine), trimesic aldehyde and trifluoroethanol according to the mass ratio of 35:10:55, coating the solution on the treated substrate by adopting a drop coating method, standing the substrate in an environment of 40 ℃ for 3 hours to slowly volatilize the solvent, transferring the substrate to an environment of 80 ℃ and heating the substrate for 9 hours to form a cross-linked film, thus obtaining the betaine type amphiphilic polymer antifogging and antibacterial coating with stable structure.
The structural formula of the trimesic aldehyde is as follows:
experiments show that the coating has good antifogging property, and the light transmittance is 89.8%. The coating bacteriostasis rate is 98.5%.
Example 4
The amphiphilic polymer antifogging antibacterial coating containing betaine zwitterions comprises the following components in percentage by mass:
poly (alkyl methacrylate-co-2-aminoethyl methacrylate-co-methacryloylethyl betaine): 50 percent;
aromatic polyaldehydes: 5 percent;
solvent: 45 percent.
(1) Preparation of poly (n-octyl methacrylate-co-2-aminoethyl methacrylate-co-methacryloylethyl sulfobetaine):
weighing medicines serving as solutes and dissolving the medicines into a trifluoroethanol solvent according to the molar ratio of 20:40:40 to obtain a solution with the mass fraction of the solutes of 20%, and adding an initiator azodiisobutyronitrile with the mass equal to 1% of the mass of the solutes. Sealing the reactants in a Schlenk bottle, performing freeze-thaw cycle for three times, heating in an oil bath at 70 ℃ for 11 hours to perform free radical polymerization to obtain poly (n-octyl methacrylate-co-2-aminoethyl methacrylate-co-methacryloylethyl sulfobetaine), wherein the structural formula of the poly (n-octyl methacrylate-co-2-aminoethyl methacrylate-co-methacryloylethyl sulfobetaine) is as follows:
(2) preparing the stable betaine amphiphilic polymer antifogging antibacterial coating:
and (3) carrying out plasma treatment on the glass sheet, soaking the glass sheet in a 15% methanol solution of (3-aminopropyl) trimethoxy silane for 10 hours, respectively carrying out ultrasonic treatment on the glass sheet for 5min by using methanol and ethanol, and drying to obtain the glass substrate with the aminated surface. Preparing solution from poly (n-octyl methacrylate-co-methacrylic acid-2-aminoethyl ester-co-methacryloyl ethyl sulfobetaine), trimesic aldehyde and tetrahydrofuran according to the mass ratio of 50:5:45, coating the solution on the treated substrate by adopting a spraying method, standing the substrate in an environment of 40 ℃ for 4 hours to slowly volatilize the solvent, transferring the substrate to an environment of 90 ℃ and heating the substrate for 10 hours to form a film by crosslinking, thus obtaining the betaine type amphiphilic polymer antifogging and antibacterial coating with stable structure.
The structural formula of the trimesic aldehyde is as follows:
experiments show that the coating has good antifogging property, and the light transmittance is 89.5%. As shown in the figure I, compared with the right figure, the number of colonies in the left figure is greatly reduced, which shows that the coating can kill most bacteria in suspension and inhibit the growth of residual bacteria, and has good antibacterial performance, and the calculated antibacterial rate of the coating is 98.0%.
Example 5
The amphiphilic polymer antifogging antibacterial coating containing betaine zwitterions comprises the following components in percentage by mass:
poly (alkyl methacrylate-co-2-aminoethyl methacrylate-co-methacryloylethyl betaine): 70 percent;
aromatic polyaldehydes: 2 percent;
solvent: 28 percent.
(1) Preparation of poly (lauryl methacrylate-co-2-aminoethyl methacrylate-co-methacryloylethyl carboxybetaine):
weighing medicines serving as solutes and dissolving lauryl methacrylate, methacrylic acid-2-aminoethyl hydrochloride and methacrylic acid dimethyl propyl aminoethyl carboxylate in a molar ratio of 10:50:40 into a trifluoroethanol solvent to prepare a solution with the mass fraction of the solutes of 30%, and adding an initiator azodiisobutyronitrile with the mass equal to 1% of the mass of the solutes. Sealing the reactants in a Schlenk bottle, performing freeze-thaw cycle for three times, heating in an oil bath at 75 ℃ for 11 hours to perform free radical polymerization to obtain poly (lauryl methacrylate-co-2-aminoethyl methacrylate-co-methacryloylethylcarboxy betaine), wherein the structural formula of the poly (lauryl methacrylate-co-methacrylic acid-2-aminoethyl methacrylate-co-methacryloylethylcarboxy betaine) is as follows:
(2) preparing the stable betaine amphiphilic polymer antifogging antibacterial coating:
and (3) carrying out plasma treatment on the glass sheet, soaking the glass sheet in 20% methanol solution of (3-aminopropyl) trimethoxy silane for 10h, respectively carrying out ultrasonic treatment on the glass sheet for 5min by using methanol and ethanol, and drying to obtain the glass substrate with the aminated surface. Preparing solution from poly (lauryl methacrylate-co-methacrylic acid-2-aminoethyl ester-co-methacryloyl ethyl carboxyl betaine), m-phthalaldehyde and a methanol/trifluoroethanol mixed solvent according to a mass ratio of 70:2:28, coating the solution on the treated substrate by a dip coating method, standing the substrate in an environment at 50 ℃ for 4 hours to slowly volatilize the solvent, transferring the substrate to an environment at 80 ℃ and heating the substrate for 10 hours to form a film by crosslinking, thus obtaining the betaine amphiphilic polymer antifogging and antibacterial coating with a stable structure.
The structural formula of the isophthalaldehyde used is as follows:
experiments show that the coating has good antifogging property, and the light transmittance is 89.2%. The coating bacteriostasis rate is 98.4%.
Example 6
The amphiphilic polymer antifogging antibacterial coating containing betaine zwitterions comprises the following components in percentage by mass:
poly (alkyl methacrylate-co-2-aminoethyl methacrylate-co-methacryloylethyl betaine): 70 percent;
aromatic polyaldehydes: 0.5 percent;
solvent: 29.5 percent.
(1) Preparation of poly (octadecyl methacrylate-co-2-aminoethyl methacrylate-co-methacryloylethyl sulfobetaine):
the preparation method comprises the steps of weighing medicines serving as solutes and dissolving the medicines in a trifluoroethanol solvent according to the molar ratio of 10:70:20, namely octadecyl methacrylate, methacrylic acid-2-aminoethyl ester hydrochloride and methacrylic acid dimethyl propyl ammonium sulfonate to prepare a solution with the mass fraction of the solutes of 40%, and adding an initiator azodiisobutyronitrile with the mass equal to 1% of the mass of the solutes. Sealing the reactants in a Schlenk bottle, performing freeze-thaw cycle for three times, heating in an oil bath at 80 ℃ for 12 hours to perform free radical polymerization to obtain poly (octadecyl methacrylate-co-2-aminoethyl methacrylate-co-methacryloylethyl sulfobetaine), wherein the structural formula of the poly (octadecyl methacrylate-co-methacrylic acid-2-aminoethyl ester-co-methacryloylethyl sulfobetaine) is as follows:
(2) preparing the stable betaine amphiphilic polymer antifogging antibacterial coating:
and (3) carrying out plasma treatment on the glass sheet, soaking the glass sheet in 20% methanol solution of (3-aminopropyl) trimethoxy silane for 10h, respectively carrying out ultrasonic treatment on the glass sheet for 5min by using methanol and ethanol, and drying to obtain the glass substrate with the aminated surface. Preparing a solution from poly (octadecyl methacrylate-co-methacrylic acid-2-aminoethyl ester-co-methacryloyl ethyl sulfobetaine), o-phthalaldehyde and an ethanol/tetrahydrofuran mixed solvent according to a mass ratio of 70:0.5:29.5, coating the solution on the treated substrate by a drop coating method, standing the substrate in an environment at 50 ℃ for 5 hours to slowly volatilize the solvent, transferring the substrate to an environment at 100 ℃ and heating the substrate for 10 hours to form a cross-linked film, thus obtaining the betaine type amphiphilic polymer antifogging and antibacterial coating with a stable structure.
The structural formula of the o-phthalaldehyde is as follows:
experiments show that the coating has good antifogging property, and the light transmittance is 88.3%. The bacteriostatic rate of the coating is 99.7%.
While the methods and techniques of the present invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and/or modifications of the methods and techniques described herein may be made without departing from the spirit and scope of the invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and content of the invention.
Claims (9)
1. An amphiphilic polymer antifogging antibacterial coating containing betaine zwitterions is characterized by comprising the following components in percentage by mass:
poly (alkyl methacrylate-co-2-aminoethyl methacrylate-co-methacryloylethyl betaine): 2-70%;
aromatic polyaldehydes: 0.5-20%;
solvent: and (4) the balance.
2. The anti-fog antimicrobial coating of claim 1, wherein the poly (alkyl methacrylate-co-2-aminoethyl methacrylate-co-methacryloylethylbetaine) has the formula:
a is 10-20, b is 40-80, c is 10-40, and n is 0-17; a, b, c and n are integers;
r is
3. The anti-fog, anti-bacterial coating of claim 1, wherein the aromatic polyaldehyde has the formula:
4. the anti-fog anti-bacterial coating of claim 1, wherein the poly (alkyl methacrylate-co-2-aminoethyl methacrylate-co-methacryloylethylbetaine) is prepared by the following method:
weighing the alkyl methacrylate, 2-aminoethyl methacrylate hydrochloride and methacryloyl ethyl betaine according to the mol ratio of (10-20) to (40-80) to (10-40), dissolving the substances in a trifluoroethanol solvent to prepare a 10-40% solution, adding 1 wt% of an initiator azobisisobutyronitrile, placing the solution in a Schlenk bottle for reaction, performing freeze-thaw cycle for three times, heating the solution in an oil bath at 60-80 ℃ for 10-12 hours for free radical polymerization, adding a small amount of sodium hydroxide after the reaction is finished until the pH of the solution is 9, and dialyzing the solution in deionized water for three days.
5. The preparation method of the amphiphilic polymer antifogging and antibacterial coating containing the betaine zwitterion as claimed in claim 1, is characterized in that the preparation method of the coating comprises the following steps: preparing a solution from poly (alkyl methacrylate-co-methacrylic acid-2-aminoethyl ester-co-methacryloyl ethyl betaine), aromatic polyaldehyde and a solvent according to the mass percentage, coating the solution on the surface of a modified glass substrate, drying the surface at the temperature of 20-50 ℃ for 1-5 hours to remove the solvent, transferring the surface to the temperature of 70-100 ℃ and heating the surface for 5-10 hours to perform crosslinking, thus obtaining the antifogging antibacterial coating.
6. The method of claim 5, wherein the coating method is one of drop coating, spin coating, spray coating, or dip coating.
7. The method according to claim 5, wherein the surface modification method of the base material comprises: firstly, carrying out plasma treatment on a glass sheet, then soaking the glass sheet in a 1-20% methanol solution of a silane coupling agent for 2-10 h, finally respectively carrying out ultrasonic treatment on the glass sheet for 5min by using methanol and ethanol, and drying the glass sheet at room temperature.
8. The method according to claim 5, wherein the solvent is one of trifluoroethanol, methanol, tetrahydrofuran, and ethanol, or a mixed solvent thereof.
9. The method according to claim 7, wherein the silane coupling agent is (3-aminopropyl) trimethoxysilane.
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