CN110437660B - Preparation method and application of aromatic polyaldehyde crosslinked polydimethylsiloxane-containing segmented copolymer coating - Google Patents
Preparation method and application of aromatic polyaldehyde crosslinked polydimethylsiloxane-containing segmented copolymer coating Download PDFInfo
- Publication number
- CN110437660B CN110437660B CN201910668682.6A CN201910668682A CN110437660B CN 110437660 B CN110437660 B CN 110437660B CN 201910668682 A CN201910668682 A CN 201910668682A CN 110437660 B CN110437660 B CN 110437660B
- Authority
- CN
- China
- Prior art keywords
- coating
- solution
- polydimethylsiloxane
- polyethylene glycol
- poly
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
-
- 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
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
-
- 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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
- C08G81/025—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyether sequences
-
- 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
- C09D187/00—Coating compositions based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
- C09D187/005—Block or graft polymers not provided for in groups C09D101/00 - C09D185/04
-
- 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
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- 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
- C08F2438/00—Living radical polymerisation
- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
Abstract
The invention relates to a preparation method and application of an aromatic polyaldehyde crosslinked polydimethylsiloxane-containing segmented copolymer coating. Preparing PDMS-b-poly (2-aminoethyl methacrylate-b-polyethylene glycol methacrylate), aromatic polyaldehyde and a solvent into a solution according to mass percent, coating the solution on the surface of the modified glass substrate, drying the solution at the temperature of 20-50 ℃ for 1-5 hours to remove the solvent, transferring the solution to the temperature of 70-100 ℃ and heating the solution for 5-10 hours to perform crosslinking, thereby obtaining the antifogging antibacterial self-repairing coating. The invention also provides a preparation method of PDMS-b-poly (2-aminoethyl methacrylate-b-polyethylene glycol methacrylate). The copolymer coating has the functions of antifogging, antibiosis and self-repairing, the preparation method of the coating is simple, the limitation that the common coating material cannot adapt to the environment due to single function and cannot normally work or needs frequent replacement is broken through, and the coating has practical application value.
Description
Technical Field
The invention relates to a preparation method and application of an aromatic polyaldehyde crosslinked polydimethylsiloxane-containing segmented copolymer coating, belonging to the field of high polymer coating materials.
Background
In life and production, transparent optical devices such as optical lenses, glass cases, prisms and the like need to maintain good transparency of materials in environments with high humidity or large temperature difference between cold and hot temperatures. In order to ensure good light transmission, a transparent coating layer having an antifogging function is usually coated on the surface of the transparent coating layer. However, after long-term use under special conditions, the surface of the coating often grows bacteria or is scratched or abraded, so that the coating loses the normal light transmission capability, and the anti-fog performance of the coating is affected, therefore, the preparation of the anti-fog coating with the functions of antibiosis and self-repair is necessary.
Ding et al used a crosslinked structure formed by Schiff base bonds and formed an antifog coating having a self-repairing function by self-assembly layer by layer (Hu B, Chen L, Lan S, Ren P, Wu S, Liu X, Shi X, Li H, Du Y, Ding F.Layer-by-layer assembly of a polysaccharide film with self-repairing and anti-engineering properties for a food packaging application, Applied Nano Materials,2018,1(7):3733-3740), and the results showed that the coating could complete self-repairing in a shorter time. However, the method for preparing the coating by layer-by-layer self-assembly is complex in process, and the prepared coating has no antibacterial property and is difficult to resist the breeding of bacteria.
Disclosure of Invention
The invention aims to provide a preparation method and application of an aromatic polyaldehyde crosslinked polydimethylsiloxane-containing segmented copolymer coating. The copolymer coating has the functions of fog prevention, antibiosis and self-repairing, and belongs to the field of high polymer coating materials. The invention uses chain transfer agent of Polydimethylsiloxane (PDMS) to synthesize amphiphilic block copolymer PDMS-b-poly (2-aminoethyl methacrylate-b-polyethylene glycol methacrylate) with uniform molecular weight by reversible addition-fragmentation chain transfer polymerization (RAFT) method, and the amphiphilic block copolymer PDMS-b-poly (2-aminoethyl methacrylate-b-polyethylene glycol methacrylate) is crosslinked by aromatic polyaldehyde to prepare the transparent coating with multiple functions. The PDMS is a molecular chain formed by a silica framework, has hydrophobicity, and can obviously improve the stability of the coating; the low molecular weight polyethylene glycol methacrylate has good hydrophilicity, can provide excellent antifogging performance for the coating, and a hydration layer formed on the surface of the coating makes bacteria difficult to adhere to the surface of the coating, so that an antibacterial effect is achieved; the amino group in aminoethyl methacrylate can undergo a crosslinking reaction with aromatic polyaldehydes to form a stable structure that is difficult to break in water or high humidity environments. In addition, the Schiff base obtained by the reaction of the amino and the aldehyde group has a reversible imine bond, and when polyethylene glycol methacrylate and polydimethylsiloxane with low glass transition temperature exist in a molecular chain, the coating can be self-repaired at relatively low temperature. The material can simultaneously realize the functions of fog prevention, bacteria resistance and self-repairing through simple components and a preparation method, has extremely wide application field and high practical application value.
The invention relates to an aromatic polyaldehyde crosslinked polydimethylsiloxane-containing segmented copolymer coating which is characterized by comprising the following components in percentage by mass:
PDMS-b-poly (2-aminoethyl methacrylate-b-polyethylene glycol methacrylate): 2-70%;
aromatic polyaldehydes: 0.5-20%;
solvent: and (4) the balance.
Wherein the aromatic polyaldehyde is o-phthalaldehyde or m-phthalaldehyde or trimesic aldehyde.
The structural formula of the PDMS-b-poly (2-aminoethyl methacrylate-b-polyethylene glycol methacrylate) is as follows:
wherein x is 20-80, y is 20-80, and n is 2-100. x, y and n are integers.
Wherein R has a structural formula
Wherein m is 10-20. m is an integer.
The structural formula of the aromatic polyaldehyde is as follows:
the synthesis method of the PDMS-b-poly (2-aminoethyl methacrylate-b-polyethylene glycol methacrylate) comprises the following steps:
(1) preparation of Polydimethylsiloxane (PDMS) macromolecular reversible addition-fragmentation chain transfer agent:
dissolving single-ended hydroxy polydimethylsiloxane (PDMS-OH), 4-cyano-4- (thiobenzoyl) valeric acid (CPADB), Dicyclohexylcarbodiimide (DCC) and 4-Dimethylaminopyridine (DMAP) in a molar ratio of 1 (1-2) to (1-3) to (0.2-0.8) in dichloromethane to prepare a solution with the mass fraction of 10-50%, and reacting for 10-48 h under the protection of nitrogen; after the reaction is finished, precipitating and separating the crude product by using methanol, and finally drying the crude product in a vacuum oven for 10-24 hours to obtain a PDMS chain transfer agent;
(2) preparation of PDMS-b-Polymethylaminoethyl methacrylate Block copolymer:
weighing 2-aminoethyl methacrylate hydrochloride monomer, initiator Azobisisobutyronitrile (AIBN) and PDMS chain transfer agent in a molar ratio of (20-80): 1:0.2, sequentially adding into trifluoroethanol to prepare a solution with a mass fraction of 10-50%, heating in an oil bath at 60-80 ℃ under a nitrogen atmosphere for 10-12 h for polymerization, then adding a small amount of NaOH solution into the reacted solution until the pH value is 9, dialyzing in deionized water for three days, and freeze-drying to obtain PDMS-b-polymethacrylic acid-2-aminoethyl ester;
(3) preparation of PDMS-b-poly (2-aminoethyl methacrylate-b-polyethylene glycol methacrylate) block copolymer:
adding the obtained PDMS-b-poly (2-aminoethyl methacrylate-b-polyethylene glycol methacrylate) and AIBN into trifluoroethanol according to the molar ratio of 1 (20-80): 0.2, heating in an oil bath at 60-80 ℃ under the atmosphere of nitrogen for 10-12 h for polymerization, dialyzing the product in deionized water for three days, and freeze-drying to obtain PDMS-b-poly (2-aminoethyl methacrylate-b-polyethylene glycol methacrylate).
The preparation method of the aromatic polyaldehyde crosslinked polydimethylsiloxane-containing block copolymer coating comprises the following steps:
preparing PDMS-b-poly (2-aminoethyl methacrylate-b-polyethylene glycol methacrylate), aromatic polyaldehyde and a solvent into a solution according to the mass percentage, coating the solution on the surface of the modified glass substrate, drying the solution at the temperature of 20-50 ℃ for 1-5 hours to remove the solvent, transferring the solution to the temperature of 70-100 ℃ and heating the solution for 5-10 hours to perform crosslinking, thereby obtaining the antifogging antibacterial self-repairing 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 aromatic polyaldehyde crosslinked polydimethylsiloxane-containing segmented copolymer coating is one or a mixed solvent of trifluoroethanol, methanol, tetrahydrofuran and ethanol.
The method for testing the water contact angle, the antibacterial property and the self-repairing property comprises the following steps:
water contact angle test: 5 mul of deionized water was dropped onto the coating surface and the contact angle values were read using a five point fitting method and averaged 5 times for each coating measurement. The measurement result is between 60 and 80 degrees, which shows that the surface of the coating has good amphipathy.
And (3) testing antibacterial performance: and (3) 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 out and washing the coating for three times, placing the coating into 4mL of sterile water, performing ultrasonic treatment for 5 minutes, taking out 10 mu L of ultrasonic suspension, dropwise adding the suspension onto a solid culture medium, culturing for 16 hours at 37 ℃, taking out, counting the number of bacterial colonies on the solid culture medium, and calculating the anti-adhesion rate.
Self-repairing performance test: cutting a scratch on the surface of the coating by using a razor blade, dripping water at the cut position by using a syringe, observing whether the scratch disappears after a period of time, and judging whether the coating has self-repairability. Through testing, the coating has good self-repairing performance.
The invention relates to an amphiphilic coating which is obtained by crosslinking and film-forming a block polymer containing PDMS at the chain end, and is characterized by having antifogging, antibacterial and self-repairing properties. The preparation method of the coating is simple, can be applied to complex environments, breaks through the limitation that the common coating material cannot adapt to the environment due to single function, cannot work normally or needs to be replaced frequently, and has practical application value.
Detailed Description
The technical solution of the present invention is further explained below with reference to the embodiments.
Example 1
The aromatic polyaldehyde crosslinked polydimethylsiloxane-containing segmented copolymer coating comprises the following components in percentage by mass:
PDMS-b-poly (2-aminoethyl methacrylate-b-polyethylene glycol methacrylate): 2 percent;
aromatic polyaldehydes: 0.5 percent;
solvent: 97.5 percent.
(1) Preparation of PDMS-b-poly (2-aminoethyl methacrylate-b-polyethylene glycol methacrylate):
dissolving single-end hydroxyl polydimethylsiloxane (PDMS-OH), 4-cyano-4- (thiobenzoyl) pentanoic acid (CPADB), Dicyclohexylcarbodiimide (DCC) and 4-Dimethylaminopyridine (DMAP) in a proper amount of dichloromethane according to a molar ratio of 1:1:1:0.2 to prepare a solution with the mass fraction of 10%, and reacting for 10 hours under the protection of nitrogen. After the reaction is finished, precipitating and separating a crude product by using methanol, and finally drying the crude product in a vacuum oven for 10 hours to obtain the PDMS chain transfer agent.
Weighing 2-aminoethyl methacrylate hydrochloride monomer, initiator Azobisisobutyronitrile (AIBN) and PDMS chain transfer agent in a molar ratio of 20:1:0.2, sequentially adding into trifluoroethanol to prepare a solution with a mass fraction of 10%, heating in an oil bath at 60 ℃ for 10h under a nitrogen atmosphere for polymerization, adding a small amount of NaOH solution into the reacted solution until the pH value is 9, dialyzing in deionized water for three days, and freeze-drying to obtain PDMS-b-poly (2-aminoethyl methacrylate).
Adding the obtained PDMS-b-poly (2-aminoethyl methacrylate), polyethylene glycol methacrylate monomer (molecular weight 2) and AIBN into trifluoroethanol according to the molar ratio of 1:80:0.2, heating in an oil bath at 60 ℃ under the nitrogen atmosphere for 10h for polymerization, dialyzing the product in deionized water for three days, and freeze-drying to obtain PDMS-b-poly (2-aminoethyl methacrylate-b-polyethylene glycol methacrylate), wherein the structural formula is as follows:
wherein R has a structural formula
(2) The preparation method of the aromatic polyaldehyde crosslinked polydimethylsiloxane-containing block copolymer coating comprises the following steps:
firstly, carrying out plasma treatment on a glass sheet, then soaking the glass sheet in a 1% methanol solution of a silane coupling agent for 2 hours, 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. PDMS-b-poly (methacrylic acid-2-aminoethyl ester-b-polyethylene glycol methacrylate), o-phthalaldehyde and methanol are prepared into solution according to the ratio of 2:0.5:97.5, the solution is dipped and coated on the surface of the modified glass substrate, the solution is removed by drying for 1h at the temperature of 20 ℃, and then the solution is transferred to the temperature of 70 ℃ and heated for 5h for crosslinking, so that the antifogging and antibacterial coating is obtained. The structural formula of the o-phthalaldehyde is as follows:
after the experiment, the water contact angle of the coating is 63.5 +/-2.7 degrees. The anti-adhesion rate of the coating was 94.7%. The self-repairing performance of the coating is good.
Example 2
The aromatic polyaldehyde crosslinked polydimethylsiloxane-containing segmented copolymer coating comprises the following components in percentage by mass:
PDMS-b-poly (2-aminoethyl methacrylate-b-polyethylene glycol methacrylate): 20 percent;
aromatic polyaldehydes: 5 percent;
solvent: 75 percent.
(1) Preparation of PDMS-b-poly (2-aminoethyl methacrylate-b-polyethylene glycol methacrylate):
dissolving single-end hydroxyl polydimethylsiloxane (PDMS-OH), 4-cyano-4- (thiobenzoyl) pentanoic acid (CPADB), Dicyclohexylcarbodiimide (DCC) and 4-Dimethylaminopyridine (DMAP) in a proper amount of dichloromethane according to a molar ratio of 1:1:2:0.3 to prepare a solution with the mass fraction of 20%, and reacting for 12 hours under the protection of nitrogen. After the reaction is finished, precipitating and separating a crude product by using methanol, and finally drying the crude product in a vacuum oven for 12 hours to obtain the PDMS chain transfer agent.
Weighing 2-aminoethyl methacrylate hydrochloride monomer, initiator Azobisisobutyronitrile (AIBN) and PDMS chain transfer agent in a molar ratio of 40:1:0.2, sequentially adding into trifluoroethanol to prepare a solution with a mass fraction of 20%, heating in an oil bath at 65 ℃ for 10h under a nitrogen atmosphere for polymerization, adding a small amount of NaOH solution into the reacted solution until the pH value is 9, dialyzing in deionized water for three days, and freeze-drying to obtain PDMS-b-poly (2-aminoethyl methacrylate).
Adding the obtained PDMS-b-poly (2-aminoethyl methacrylate) -b-polyethylene glycol methacrylate monomer (molecular weight 10) and AIBN into trifluoroethanol according to the molar ratio of 1:60:0.2, heating in an oil bath at 65 ℃ under the nitrogen atmosphere for 10h for polymerization, dialyzing the product in deionized water for three days, and freeze-drying to obtain PDMS-b-poly (2-aminoethyl methacrylate-b-polyethylene glycol methacrylate), wherein the structural formula is as follows:
wherein R has a structural formula
(2) The preparation method of the aromatic polyaldehyde crosslinked polydimethylsiloxane-containing block copolymer coating comprises the following steps:
firstly, carrying out plasma treatment on a glass sheet, then soaking the glass sheet in a 5% methanol solution of a silane coupling agent for 5 hours, finally respectively carrying out ultrasonic treatment on the glass sheet for 5 minutes by using methanol and ethanol, and drying the glass sheet at room temperature. PDMS-b-poly (methacrylic acid-2-aminoethyl ester-b-polyethylene glycol methacrylate), m-phthalaldehyde and ethanol are prepared into a solution according to the ratio of 20:5:75, the solution is dripped on the surface of a modified glass substrate, the modified glass substrate is dried at the temperature of 20 ℃ for 2 hours to remove the solvent, and then the modified glass substrate is transferred to the temperature of 75 ℃ for heating for 6 hours to carry out crosslinking, so that the antifogging and antibacterial coating is obtained. The structural formula of the isophthalaldehyde used is as follows:
after the experiment, the water contact angle of the coating is 68.3 +/-4.0 degrees. The anti-adhesion rate of the coating is 96.4%. The self-repairing performance of the coating is good.
Example 3
The aromatic polyaldehyde crosslinked polydimethylsiloxane-containing segmented copolymer coating comprises the following components in percentage by mass:
PDMS-b-poly (2-aminoethyl methacrylate-b-polyethylene glycol methacrylate): 40 percent;
aromatic polyaldehydes: 10 percent;
solvent: 50 percent.
(1) Preparation of PDMS-b-poly (2-aminoethyl methacrylate-b-polyethylene glycol methacrylate):
dissolving single-end hydroxyl polydimethylsiloxane (PDMS-OH), 4-cyano-4- (thiobenzoyl) pentanoic acid (CPADB), Dicyclohexylcarbodiimide (DCC) and 4-Dimethylaminopyridine (DMAP) in a proper amount of dichloromethane according to a molar ratio of 1:1:2:0.4 to prepare a solution with the mass fraction of 30%, and reacting for 24 hours under the protection of nitrogen. After the reaction is finished, precipitating and separating a crude product by using methanol, and finally, putting the crude product into a vacuum oven to dry for 15 hours to obtain the PDMS chain transfer agent.
Weighing 2-aminoethyl methacrylate hydrochloride monomer, initiator Azobisisobutyronitrile (AIBN) and PDMS chain transfer agent in a molar ratio of 50:1:0.2, sequentially adding into trifluoroethanol to prepare a solution with a mass fraction of 30%, heating in an oil bath at 70 ℃ under a nitrogen atmosphere for 11h for polymerization, adding a small amount of NaOH solution into the reacted solution until the pH value is 9, dialyzing in deionized water for three days, and freeze-drying to obtain PDMS-b-aminoethyl methacrylate.
Adding the obtained PDMS-b-poly (2-aminoethyl methacrylate) -b-polyethylene glycol methacrylate monomer (molecular weight is 30) and AIBN into trifluoroethanol according to the molar ratio of 1:50:0.2, heating in an oil bath at 70 ℃ under the nitrogen atmosphere for 11h for polymerization, dialyzing the product in deionized water for three days, and freeze-drying to obtain PDMS-b-poly (2-aminoethyl methacrylate-b-polyethylene glycol methacrylate), wherein the structural formula is as follows:
wherein R has a structural formula
(2) The preparation method of the aromatic polyaldehyde crosslinked polydimethylsiloxane-containing block copolymer coating comprises the following steps:
firstly, carrying out plasma treatment on a glass sheet, then soaking the glass sheet in a 10% methanol solution of a silane coupling agent for 8 hours, 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. PDMS-b-poly (methacrylic acid-2-aminoethyl ester-b-polyethylene glycol methacrylate), trimesic aldehyde and trifluoroethanol are prepared into a solution according to the ratio of 40:10:50, the solution is coated on the surface of the modified glass substrate in a dip-coating manner, the solution is dried for 2h at the temperature of 30 ℃ to remove the solvent, and then the solution is transferred to the temperature of 80 ℃ to be heated for 7h for crosslinking, so that the antifogging and antibacterial coating is obtained. The structural formula of the trimesic aldehyde is as follows:
after the experiment, the water contact angle of the coating is 72.2 +/-2.8 degrees. The anti-adhesion rate of the coating was 97.9%. The self-repairing performance of the coating is good.
Example 4
The aromatic polyaldehyde crosslinked polydimethylsiloxane-containing segmented copolymer coating comprises the following components in percentage by mass:
PDMS-b-poly (2-aminoethyl methacrylate-b-polyethylene glycol methacrylate): 50 percent;
aromatic polyaldehydes: 15 percent;
solvent: 35 percent.
(1) Preparation of PDMS-b-poly (2-aminoethyl methacrylate-b-polyethylene glycol methacrylate):
dissolving single-end hydroxyl polydimethylsiloxane (PDMS-OH), 4-cyano-4- (thiobenzoyl) pentanoic acid (CPADB), Dicyclohexylcarbodiimide (DCC) and 4-Dimethylaminopyridine (DMAP) in a proper amount of dichloromethane according to a molar ratio of 1:2:3:0.5 to prepare a solution with the mass fraction of 40%, and reacting for 24 hours under the protection of nitrogen. After the reaction is finished, precipitating and separating a crude product by using methanol, and finally drying the crude product in a vacuum oven for 18 hours to obtain the PDMS chain transfer agent.
Weighing 2-aminoethyl methacrylate hydrochloride monomer, initiator Azobisisobutyronitrile (AIBN) and PDMS chain transfer agent in a molar ratio of 60:1:0.2, sequentially adding into trifluoroethanol to prepare a solution with a mass fraction of 40%, heating in an oil bath at 75 ℃ under a nitrogen atmosphere for 11h for polymerization, adding a small amount of NaOH solution into the reacted solution until the pH value is 9, dialyzing in deionized water for three days, and freeze-drying to obtain PDMS-b-poly (2-aminoethyl methacrylate).
Adding the obtained PDMS-b-poly (2-aminoethyl methacrylate) -b-polyethylene glycol methacrylate monomer (molecular weight is 50) and AIBN into trifluoroethanol according to the molar ratio of 1:40:0.2, heating in an oil bath at 75 ℃ under the nitrogen atmosphere for 11h for polymerization, dialyzing the product in deionized water for three days, and freeze-drying to obtain PDMS-b-poly (2-aminoethyl methacrylate-b-polyethylene glycol methacrylate), wherein the structural formula is as follows:
wherein R has a structural formula
(2) The preparation method of the aromatic polyaldehyde crosslinked polydimethylsiloxane-containing block copolymer coating comprises the following steps:
firstly, carrying out plasma treatment on a glass sheet, then soaking the glass sheet in a 15% methanol solution of a silane coupling agent for 10 hours, 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. PDMS-b-poly (methacrylic acid-2-aminoethyl ester-b-polyethylene glycol methacrylate), trimesic aldehyde and tetrahydrofuran are prepared into solution according to the ratio of 50:15:35, the solution is sprayed on the surface of a modified glass substrate, the surface is dried for 3h at the temperature of 35 ℃ to remove the solvent, and then the surface is transferred to the temperature of 85 ℃ to be heated for 8h for crosslinking, so that the antifogging and antibacterial coating is obtained. The structural formula of the trimesic aldehyde is as follows:
after the experiment, the water contact angle of the coating is 75.8 +/-3.2 degrees. The anti-adhesion rate of the coating is 98.2%. The self-repairing performance of the coating is good.
Example 5
The aromatic polyaldehyde crosslinked polydimethylsiloxane-containing segmented copolymer coating comprises the following components in percentage by mass:
PDMS-b-poly (2-aminoethyl methacrylate-b-polyethylene glycol methacrylate): 60 percent;
aromatic polyaldehydes: 17 percent;
solvent: 23 percent.
(1) Preparation of PDMS-b-poly (2-aminoethyl methacrylate-b-polyethylene glycol methacrylate):
dissolving single-end hydroxyl polydimethylsiloxane (PDMS-OH), 4-cyano-4- (thiobenzoyl) pentanoic acid (CPADB), Dicyclohexylcarbodiimide (DCC) and 4-Dimethylaminopyridine (DMAP) in a proper amount of dichloromethane according to a molar ratio of 1:2:1:0.6 to prepare a solution with the mass fraction of 40%, and reacting for 36 hours under the protection of nitrogen. After the reaction is finished, precipitating and separating a crude product by using methanol, and finally drying the crude product in a vacuum oven for 24 hours to obtain the PDMS chain transfer agent.
Weighing 2-aminoethyl methacrylate hydrochloride monomer, initiator Azobisisobutyronitrile (AIBN) and PDMS chain transfer agent in a molar ratio of 70:1:0.2, sequentially adding into trifluoroethanol to prepare a solution with a mass fraction of 50%, heating in an oil bath at 80 ℃ for 12h under a nitrogen atmosphere for polymerization, adding a small amount of NaOH solution into the reacted solution until the pH value is 9, dialyzing in deionized water for three days, and freeze-drying to obtain PDMS-b-poly (2-aminoethyl methacrylate).
Adding the obtained PDMS-b-poly (2-aminoethyl methacrylate) -b-polyethylene glycol methacrylate monomer (molecular weight 80) and AIBN into trifluoroethanol according to the molar ratio of 1:30:0.2, heating in an oil bath at 80 ℃ under the nitrogen atmosphere for 12h for polymerization, dialyzing the product in deionized water for three days, and freeze-drying to obtain PDMS-b-poly (2-aminoethyl methacrylate-b-polyethylene glycol methacrylate), wherein the structural formula is as follows:
wherein R has a structural formula
(2) The preparation method of the aromatic polyaldehyde crosslinked polydimethylsiloxane-containing block copolymer coating comprises the following steps:
firstly, carrying out plasma treatment on a glass sheet, then soaking the glass sheet in a 20% methanol solution of a silane coupling agent for 10 hours, 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. PDMS-b-poly (methacrylic acid-2-aminoethyl ester-b-polyethylene glycol methacrylate), m-phthalaldehyde and methanol/trifluoroethanol are prepared into solution according to the ratio of 60:17:23, the solution is sprayed on the surface of a modified glass substrate, the surface is dried at 40 ℃ for 4h to remove the solvent, and then the surface is transferred to 90 ℃ to be heated for 9h for crosslinking, so that the antifogging and antibacterial coating is obtained. The structural formula of the isophthalaldehyde used is as follows:
after the experiment, the water contact angle of the coating is 78.3 +/-2.7 degrees. The anti-adhesion rate of the coating is 98.9%. The self-repairing performance of the coating is good.
Example 6
The aromatic polyaldehyde crosslinked polydimethylsiloxane-containing segmented copolymer coating comprises the following components in percentage by mass:
PDMS-b-poly (2-aminoethyl methacrylate-b-polyethylene glycol methacrylate): 70 percent;
aromatic polyaldehydes: 20 percent;
solvent: 10 percent.
(1) Preparation of PDMS-b-poly (2-aminoethyl methacrylate-b-polyethylene glycol methacrylate):
dissolving single-end hydroxyl polydimethylsiloxane (PDMS-OH), 4-cyano-4- (thiobenzoyl) valeric acid (CPADB), Dicyclohexylcarbodiimide (DCC) and 4-Dimethylaminopyridine (DMAP) in a molar ratio of 1:2:3:0.8 in a proper amount of dichloromethane to prepare a solution with the mass fraction of 50%, and reacting for 48 hours under the protection of nitrogen. After the reaction is finished, precipitating and separating a crude product by using methanol, and finally drying the crude product in a vacuum oven for 24 hours to obtain the PDMS chain transfer agent.
Weighing 2-aminoethyl methacrylate hydrochloride monomer, initiator Azobisisobutyronitrile (AIBN) and PDMS chain transfer agent in a molar ratio of 80:1:0.2, sequentially adding into trifluoroethanol to prepare a solution with a mass fraction of 50%, heating in an oil bath at 80 ℃ for 12h under a nitrogen atmosphere for polymerization, adding a small amount of NaOH solution into the reacted solution until the pH value is 9, dialyzing in deionized water for three days, and freeze-drying to obtain PDMS-b-aminoethyl methacrylate.
Adding the obtained PDMS-b-poly (2-aminoethyl methacrylate) -b-polyethylene glycol methacrylate monomer (molecular weight 100) and AIBN into trifluoroethanol according to the molar ratio of 1:20:0.2, heating in an oil bath at 80 ℃ under the nitrogen atmosphere for 12h for polymerization, dialyzing the product in deionized water for three days, and freeze-drying to obtain PDMS-b-poly (2-aminoethyl methacrylate-b-polyethylene glycol methacrylate), wherein the structural formula is as follows:
wherein R has a structural formula
(2) The preparation method of the aromatic polyaldehyde crosslinked polydimethylsiloxane-containing block copolymer coating comprises the following steps:
firstly, carrying out plasma treatment on a glass sheet, then soaking the glass sheet in a 20% methanol solution of a silane coupling agent for 10 hours, 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. PDMS-b-poly (methacrylic acid-2-aminoethyl ester-b-polyethylene glycol methacrylate), o-phthalaldehyde and ethanol/tetrahydrofuran are prepared into solution according to the ratio of 70:20:10, the solution is dipped and coated on the surface of the modified glass substrate, the solution is removed by drying for 5h at the temperature of 50 ℃, and then the solution is transferred to the temperature of 100 ℃ and heated for 10h for crosslinking, so that the antifogging and antibacterial coating is obtained. The structural formula of the o-phthalaldehyde is as follows:
after the experiment, the water contact angle of the coating is 80.3 +/-1.6 degrees. The anti-adhesion rate of the coating is 99.4%. The self-repairing performance of the coating is good.
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 (8)
1. The aromatic polyaldehyde crosslinked polydimethylsiloxane-containing segmented copolymer coating is characterized by comprising the following components in percentage by mass:
polydimethylsiloxane-b-poly (2-aminoethyl methacrylate-b-polyethylene glycol methacrylate): 2-70%;
aromatic polyaldehydes: 0.5-20%;
solvent: the balance;
the structural formula of the block copolymer coating, namely polydimethylsiloxane-b-poly (methacrylic acid-2-aminoethyl ester-b-polyethylene glycol methacrylate) is as follows:
x is 20-80, y is 20-80, and n is 2-100; x, y and n are integers;
r is
m＝10～20。
2. The block copolymer coating of claim 1, wherein the aromatic polyaldehyde has the formula:
3. the copolymer coating of claim 1, wherein the polydimethylsiloxane-b-poly (2-aminoethyl methacrylate-b-polyethylene glycol methacrylate) is prepared by a method comprising the steps of:
1) dissolving single-end hydroxyl polydimethylsiloxane, 4-cyano-4- (thiobenzoyl) valeric acid, dicyclohexylcarbodiimide and 4-dimethylaminopyridine into dichloromethane according to the molar ratio of 1 (1-2) to (1-3) to (0.2-0.8) to prepare a solution with the mass fraction of 10-50%, and reacting for 10-48 h under the protection of nitrogen; after the reaction is finished, precipitating and separating the crude product by using methanol, and finally drying the crude product in a vacuum oven for 10-24 hours to obtain a polydimethylsiloxane chain transfer agent;
2) weighing 2-aminoethyl methacrylate hydrochloride monomer, azodiisobutyronitrile as an initiator and a PDMS chain transfer agent in a molar ratio of (20-80): 1:0.2, sequentially adding the monomers, the azodiisobutyronitrile as the initiator and the PDMS chain transfer agent into trifluoroethanol to prepare a solution with the mass fraction of 10-50%, heating the solution in an oil bath at the temperature of 60-80 ℃ under the atmosphere of nitrogen for 10-12 h for polymerization, then adding a small amount of sodium hydroxide solution into the reacted solution until the pH value is 9, dialyzing the solution in deionized water for three days, and freeze-drying the solution to obtain polydimethylsiloxane-b-polymethacrylic acid-2-aminoethyl ester;
3) adding polydimethylsiloxane-b-polymethyl methacrylate-2-aminoethyl ester, a polyethylene glycol methacrylate monomer and azobisisobutyronitrile into trifluoroethanol according to the molar ratio of 1 (20-80): 0.2, heating in an oil bath at 60-80 ℃ under the atmosphere of nitrogen for 10-12 h for polymerization, dialyzing the product in deionized water for three days, and freeze-drying to obtain the polydimethylsiloxane-b-poly (methacrylic acid-2-aminoethyl ester-b-polyethylene glycol methacrylate).
4. The preparation method of the aromatic polyaldehyde crosslinked polydimethylsiloxane-containing block copolymer coating of claim 1, wherein polydimethylsiloxane-b-poly (2-aminoethyl methacrylate-b-polyethylene glycol methacrylate), aromatic polyaldehyde and a solvent are prepared into a solution according to the mass percentage, the solution is coated on the surface of a modified glass substrate, the surface is dried at 20-50 ℃ for 1-5 hours to remove the solvent, and then the solution is transferred to 70-100 ℃ for heating for 5-10 hours for crosslinking to obtain the antifogging antibacterial coating.
5. The method of claim 4, wherein the coating method is one of drop coating, spin coating, spray coating, or dip coating.
6. The method according to claim 4, 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.
7. The preparation method according to claim 4, wherein the solvent is one of trifluoroethanol, methanol, tetrahydrofuran, ethanol, or a mixed solvent thereof; the silane coupling agent is (3-aminopropyl) trimethoxy silane.
8. The aromatic polyaldehyde crosslinked polydimethylsiloxane-containing block copolymer coating of claim 1 is applied to the fields of antifogging, antibacterial and self-repairing coating materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910668682.6A CN110437660B (en) | 2019-07-23 | 2019-07-23 | Preparation method and application of aromatic polyaldehyde crosslinked polydimethylsiloxane-containing segmented copolymer coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910668682.6A CN110437660B (en) | 2019-07-23 | 2019-07-23 | Preparation method and application of aromatic polyaldehyde crosslinked polydimethylsiloxane-containing segmented copolymer coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110437660A CN110437660A (en) | 2019-11-12 |
| CN110437660B true CN110437660B (en) | 2021-08-27 |
Family
ID=68431345
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910668682.6A Active CN110437660B (en) | 2019-07-23 | 2019-07-23 | Preparation method and application of aromatic polyaldehyde crosslinked polydimethylsiloxane-containing segmented copolymer coating |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110437660B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| LU101497B1 (en) * | 2019-11-28 | 2021-06-01 | Luxembourg Inst Science & Tech List | Polymer conetworks of poly(pyridine-(meth)-acrylamide) derivatives-crosslinked by transition metal ions- and linked by polydimethylsiloxane derivatives |
| WO2022050361A1 (en) * | 2020-09-03 | 2022-03-10 | ダイキン工業株式会社 | Curable composition |
| JP7137105B2 (en) * | 2020-09-03 | 2022-09-14 | ダイキン工業株式会社 | silicone copolymer |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014028615A1 (en) * | 2012-08-15 | 2014-02-20 | Penn Color, Inc. | Cationic water based polymers for inkjet inks |
| CN103865014A (en) * | 2014-03-21 | 2014-06-18 | 东华大学 | Preparation method for amphipathic copolymerization network |
| CN108384293A (en) * | 2018-03-22 | 2018-08-10 | 天津大学 | A kind of antifog/anti-fog coatings and preparation method thereof based on cationic polyelectrolyte copolymer |
| CN108504150A (en) * | 2018-03-22 | 2018-09-07 | 天津大学 | A kind of anti-fog coating and preparation method thereof based on amphoteric ion polyelectrolyte copolymer |
| CN108546337A (en) * | 2018-05-16 | 2018-09-18 | 中国船舶重工集团公司第七二五研究所 | A kind of organosilicon selfreparing anti-fouling material preparation method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2957968C (en) * | 2014-08-14 | 2021-11-30 | The Governing Council Of The University Of Toronto | Biomaterial with reduced inflammatory response |
-
2019
- 2019-07-23 CN CN201910668682.6A patent/CN110437660B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014028615A1 (en) * | 2012-08-15 | 2014-02-20 | Penn Color, Inc. | Cationic water based polymers for inkjet inks |
| CN103865014A (en) * | 2014-03-21 | 2014-06-18 | 东华大学 | Preparation method for amphipathic copolymerization network |
| CN108384293A (en) * | 2018-03-22 | 2018-08-10 | 天津大学 | A kind of antifog/anti-fog coatings and preparation method thereof based on cationic polyelectrolyte copolymer |
| CN108504150A (en) * | 2018-03-22 | 2018-09-07 | 天津大学 | A kind of anti-fog coating and preparation method thereof based on amphoteric ion polyelectrolyte copolymer |
| CN108546337A (en) * | 2018-05-16 | 2018-09-18 | 中国船舶重工集团公司第七二五研究所 | A kind of organosilicon selfreparing anti-fouling material preparation method |
Non-Patent Citations (2)
| Title |
|---|
| "Comparison of Antibacterial Adhesion When Salivary;Bor-Shiunn Lee 等;《International Journal o f Molecular Sciences》;20181231;第19卷(第9期);第1-18页 * |
| " Polydimethylsiloxane-polymethacrylate block copolymers tetheringquaternary ammonium salt groups for antimicrobial coating";Xiaoshuai Qin等;《Applied Surface Science》;20151231;第328卷;第183-192页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110437660A (en) | 2019-11-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110437660B (en) | Preparation method and application of aromatic polyaldehyde crosslinked polydimethylsiloxane-containing segmented copolymer coating | |
| CN110804144B (en) | Cationic-zwitterionic block copolymers | |
| Zhang et al. | Developing self-healable and antibacterial polyacrylate coatings with high mechanical strength through crosslinking by multi-amine hyperbranched polysiloxane via dynamic vinylogous urethane | |
| CN107903734B (en) | Preparation method of water-resistant long-acting anti-fog and anti-frost high-light-transmittance coating with self-repairing performance | |
| CN110437727B (en) | N-hydroxyethyl acrylamide-based antibacterial/antifogging coating and preparation method thereof | |
| TW200951189A (en) | Silica-containing UV-crosslinkable hardcoat coatings comprising urethane acrylates | |
| Zheng et al. | A novel organic-inorganic zwitterionic acrylate polymer for high-performance anti-fog coating | |
| Wang et al. | A strategy for constructing anti-adhesion surfaces based on interfacial thiol–ene photoclick chemistry between DOPA derivatives with a catechol anchor group and zwitterionic betaine macromolecules | |
| Jia et al. | Synthesis and antibacterial investigation of cationic waterborne polyurethane containing siloxane | |
| JP5683906B2 (en) | Surface modifier | |
| KR100533905B1 (en) | Anti-fogging coating composition comprising ultra-violet light curable hydrophilic organic-inorganic hybrid materials | |
| Liu et al. | Facile casting preparation of hydrophilic coordinated PVA–Zn ion coatings with strong adhesion and high water tolerance | |
| CN108384293B (en) | Anti-fog/anti-frost coating based on cationic polyelectrolyte copolymer and preparation method thereof | |
| CN110437661B (en) | Antibacterial/antifouling/antifogging coating based on blend of quaternary ammonium salt and N-hydroxy acrylamide and preparation method thereof | |
| KR100297952B1 (en) | Coating Solution for Antifogging Properties | |
| CN114525050B (en) | Hydrophobic antifogging coating, preparation method thereof and antifogging product | |
| CN111349395A (en) | Graft modified high-molecular antifogging coating and preparation method and application method thereof | |
| CN115926614B (en) | Bionic super-hydrophilic coating with anti-frost, anti-fog and anti-fouling functions and preparation and application thereof | |
| JP5885500B2 (en) | Paint for forming transparent film and substrate with transparent film | |
| JP2005036177A (en) | Anti-fogging coating, anti-fogging molding, and production method of the anti-fogging coating | |
| JP2013124208A (en) | Anti-fog article | |
| TWI767667B (en) | Antifogging material and manufacturing method thereof | |
| CN114561128A (en) | Antifogging agent, preparation method and application thereof, and antifogging product | |
| Yang et al. | A Facile Strategy to Construct Anti‐Swelling, Antibacterial, and Antifogging Coatings for Protection of Medical Goggles | |
| CN116285550B (en) | Scratch-resistant, anti-fog and anti-icing anti-fouling hydrogel coating and preparation method thereof |
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 | ||
| CP02 | Change in the address of a patent holder | ||
| CP02 | Change in the address of a patent holder |
Address after: 300452 Binhai Industrial Research Institute Campus of Tianjin University, No. 48 Jialingjiang Road, Binhai New Area, Tianjin Patentee after: Tianjin University Address before: 300350 Haijing garden, Haihe Education Park, Jinnan, Tianjin, 135, Tianjin University. Patentee before: Tianjin University |
|
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20191112 Assignee: Tianjin Jiuhe Dingyi Technology Co.,Ltd. Assignor: Tianjin University Contract record no.: X2023120000003 Denomination of invention: Preparation and application of aromatic polyaldehyde crosslinked polydimethylsiloxane-containing block copolymer coating Granted publication date: 20210827 License type: Common License Record date: 20230109 |