CN110938359A - Method for improving antibacterial property of polyurethane coating by using hydrophilic chain extender - Google Patents
Method for improving antibacterial property of polyurethane coating by using hydrophilic chain extender Download PDFInfo
- Publication number
- CN110938359A CN110938359A CN201811116530.7A CN201811116530A CN110938359A CN 110938359 A CN110938359 A CN 110938359A CN 201811116530 A CN201811116530 A CN 201811116530A CN 110938359 A CN110938359 A CN 110938359A
- Authority
- CN
- China
- Prior art keywords
- polyurethane coating
- chain extender
- antibacterial
- hydrophilic chain
- improving
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Plant Pathology (AREA)
- Paints Or Removers (AREA)
- Polyurethanes Or Polyureas (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a method for improving antibacterial performance of a polyurethane coating by utilizing a hydrophilic chain extender. The invention overcomes the defects of the prior art, obtains the method for controlling the antibacterial performance of the cationic aqueous polyurethane coating without increasing the content of the antibacterial agent, and can improve the antibacterial capability of the coating and reduce the using amount of the antibacterial agent.
Description
Technical Field
The invention belongs to the technical field of antibacterial agent release, and particularly relates to a method for improving antibacterial performance of a polyurethane coating by using a hydrophilic chain extender, which changes the hydrophilic performance of polyurethane mixed with an antibacterial agent so as to change the release capacity of the antibacterial agent and obtain the polyurethane antibacterial coating with different antibacterial effects.
Background
Polyurethanes are generally very hydrophobic and are neither directly soluble in water nor very dispersible in water. Hydrophilic ionic groups are introduced into the molecular structure of the hydrophobic polyurethane, and then the hydrophobic polyurethane is dispersed in water to obtain the aqueous polyurethane emulsion. The cationic waterborne polyurethane is prepared by polymerizing polyisocyanate, polyol and micromolecular chain extender N-methyldiethanolamine, neutralizing with glacial acetic acid, and emulsifying. Hydrophilic groups are introduced into molecular chains of N-methyldiethanolamine, tertiary amine groups on the macromolecular chains can be converted into quaternary ammonium salts after neutralization, when the molecular chains are dispersed in water, the quaternary ammonium salts can be self-emulsified into micelles, positively charged hydrophilic groups are concentrated on the surfaces of the micelles, and hydrophobic groups are concentrated inside the micelles.
Bacteria live in every corner of our lives, seriously affecting human health. The essential conditions for the survival of the bacteria are water, nutrients and a suitable temperature. The antibacterial agent is a substance capable of killing bacteria or inhibiting the growth and reproduction of bacteria and the activity thereof, and the antibacterial coating is a coating with an antibacterial effect by adding the antibacterial agent. The antibacterial coating is widely applied to the fields of buildings, electronics and medical treatment and health. The main mode of the antibacterial material for playing the antibacterial role is that the antibacterial agent in the material is released to the contact surface, so that the antibacterial agent on the surface of the material is maintained above a certain concentration to inhibit the growth of target microorganisms. The release of the antimicrobial agent may be controlled by the degree of crosslinking of the additive within the polymer, and the release rate of the antimicrobial agent may be adjusted by varying the degree of crosslinking of the polymer matrix. The microcapsule or the nano-scale capsule can selectively control the release of the antibacterial agent, and the release of the antibacterial agent can also be controlled by changing the asymmetry and the porosity of the membrane.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for improving the antibacterial performance of a polyurethane coating by using a hydrophilic chain extender, namely a method for regulating the antibacterial performance of a cationic water-based polyurethane coating by hydrophilic and hydrophobic properties, wherein the swelling degree of a polyurethane film in water is changed by changing the content of hydrophilic groups in a polyurethane molecular chain structure, so that the release of an antibacterial agent is controlled.
The technical purpose of the invention is realized by the following technical scheme.
The method for improving the antibacterial performance of the polyurethane coating by using the hydrophilic chain extender is carried out according to the following steps:
in step 1, the molar ratio of polytetrahydrofuran diol to isophorone diisocyanate is 5: (10-13).
In step 1, polytetrahydrofuran polyether glycol is dehydrated in vacuum, and after protective gas is introduced, isophorone diisocyanate is added and mixed uniformly, and inert protective gas such as nitrogen, helium or argon is protected.
In step 1, the reaction is carried out at 80-90 ℃ for 2-3 hours.
In step 1, the catalyst is dibutyltin dilaurate in an amount of 0.05 to 0.1 parts by volume, 1ml per part by volume.
in step 2, the molar ratio of N-methyldiethanolamine to polytetrahydrofurandiol is (10-20) to (5-10).
In step 2, acetone is used in an amount of 30-40% of the mass of the prepolymer.
In step 2, the reaction is carried out at 50-60 ℃ for 3-5 hours.
In step 3, the amount of acetone is 30-40% of the mass of the system subjected to the reaction in step 2.
In step 3, glacial acetic acid is added for neutralization for a period of 30 to 60min, preferably 40 to 50 min.
In step 3, after neutralization, the system pH was 7. + -. 0.2.
And 4, dripping the water solution for dissolving and dispersing benzalkonium chloride into the system subjected to the reaction in the step 3 at a high rotating speed for emulsification, and removing acetone by rotary evaporation after the emulsification is finished to obtain the antibacterial waterborne polyurethane coating.
In step 4, the high rotation speed is 800-.
In step 4, the dosage of benzalkonium chloride is 0.1 of the mass of the system subjected to the reaction in step 3, and the dosage of benzalkonium chloride is fixed.
In the technical scheme of the invention, an oil bath is adopted for temperature control, the heating rate is 1-5 ℃/min, and the cooling rate is 1-5 ℃/min.
According to the technical scheme, polytetrahydrofuran diol, isophorone diisocyanate and a hydrophilic chain extender N-methyldiethanolamine are reacted to prepare cationic polyurethane, and then the cationic polyurethane is blended with an antibacterial agent, so that the antibacterial agent is uniformly distributed in an emulsion. And adjusting the content of N-methyldiethanolamine to prepare a series of polyurethane coatings with different hydrophilicities. After the coating is subjected to film forming and drying, the antibacterial agent is uniformly distributed in the coating, the release degree of the antibacterial agent is different, and the antibacterial capability of the coating is different. The polytetrahydrofuran diol plays a role of a soft segment in a polyurethane structure, the isophorone diisocyanate plays a role of a hard segment, and the polyurethane material has good toughness, higher strength and good adhesion to a base material. When the invention is used for preparing different hydrophilic antibacterial coatings, a cationic polyurethane system is adopted, glacial acetic acid is needed to neutralize N-methyldiethanolamine in molecular chains, the glacial acetic acid can convert most tertiary amino groups on the molecular chains into quaternary ammonium salts, the higher the content of the N-methyldiethanolamine in the coating formula is, the more the number of quaternary ammonium salt groups in the neutralized molecular chains is, the better the hydrophilicity of the molecular chains is, the better the stability of the formed emulsion is, and the larger the swelling degree of the coating in water after film forming is. The polyurethane coatings with different hydrophilicities prepared by the invention have stable state, good film-forming property and obvious antibacterial property, and the antibacterial coatings with different hydrophilicities have different antibacterial capacities.
The technical scheme of the invention is that a cationic waterborne polyurethane system is mixed with an antibacterial agent, and the hydrophilicity of polyurethane is changed by changing the content of N-methyldiethanolamine to obtain a series of waterborne polyurethane coatings with different hydrophilicities. After the polyurethane coating is formed into a film, the polyurethane coating has different swelling degrees in water, so that the polyurethane coating has different antibacterial agent release capacities, namely the swelling degree of the polyurethane coating after the film is formed is adjusted by adjusting the using amount of the hydrophilic chain extender, and the different antibacterial agent release capacities are shown (the application of the hydrophilic chain extender in the adjustment of the antibacterial agent release capacity of the polyurethane coating after the film is formed, namely the application of the hydrophilic chain extender N-methyldiethanolamine in the adjustment of the swelling degree of the polyurethane coating and/or the coating and the antibacterial agent release capacity). The antibacterial agent is the micromolecular quaternary ammonium salt, the quaternary ammonium salt can destroy the cell wall of bacteria, so that the solute in the bacteria cell flows out, the antibacterial effect is achieved, the antibacterial capacity of the coating can be changed by changing the content of the antibacterial agent, and the higher the content of the antibacterial agent is, the better the antibacterial effect is; by adopting the technical scheme of the invention, the hydrophilicity of the polyurethane is changed, and the polyurethane has high bactericidal effect under the condition of low concentration of the antibacterial agent.
Drawings
FIG. 1 is a stress-strain graph of inventive example 1.
FIG. 2 is a graph of water absorption for inventive examples 1-5.
FIG. 3 is a test chart of the inhibition zones of Escherichia coli in examples 1 to 5 of the present invention.
FIG. 4 is a test chart of the inhibition zone of Staphylococcus aureus in examples 1-5 of the present invention.
FIG. 5 is a schematic diagram of the adhesion test results of the polyurethane coating and PVC of the present invention.
Detailed Description
The technical scheme of the invention is further illustrated by combining the specific examples. Polytetrahydrofuran diol (number average molecular weight 2000), shanghai alatin Biochemical technology GmbH; isophorone diisocyanate, Shanghai Allan Biochemical technology Ltd; n-methyldiethanolamine, shanghai chinese bamboo biotechnology limited; glacial acetic acid, wind boat chemical reagents science ltd, Tianjin; acetone, tianjin yueli chemical limited; the apparatus model was TST-350 manufactured by Linkam corporation, the measuring temperature was 25 ℃, the stretching speed was 100 μm/s, and the film sample was cut into a dumbbell shape in which the effective part was 2mmX6 mm. Nitrogen is adopted for inert atmosphere protection, high rotating speed is 1200r/min for emulsification, oil bath is adopted for temperature control, the heating rate is 5 ℃/min, and the cooling rate is 5 ℃/min. 0.0027g of benzalkonium chloride, preparing 35g of aqueous solution, and dropwise adding for emulsification, wherein the uniform dropwise adding is adopted, and the use time is 20-30 min.
Example 1
0.005mol of polytetrahydrofuran diol is added into a four-neck flask provided with a thermometer and a condenser, vacuum pumping is carried out at 90 ℃ for half an hour for dehydration, the temperature is reduced to 70 ℃, 0.026mol of isophorone diisocyanate and 0.1ml of dibutyltin dilaurate are added, and the reaction is carried out for 3 hours. Cooling to below 50 ℃, adding 10g of acetone to dilute the prepolymer, adding 0.015mol of N-methyldiethanolamine, and heating to 70 ℃ for reaction for 5 hours. Cooling to below 50 ℃, adding 5g of acetone, adding 0.015mol of glacial acetic acid at normal temperature, and reacting for half an hour. 35g of deionized water containing an antibacterial agent was added dropwise from a constant pressure dropping funnel, and emulsification was carried out at a high stirring rate. Stirring for 10 minutes, and removing acetone by rotary evaporation to obtain stable emulsion with hydrophilic group content of 10% of the mass fraction of the polymer. Coating the emulsion on a polytetrafluoroethylene plate, and drying for 24h at 60 ℃ to obtain a polyurethane coating with the thickness of 0.3 mm.
Example 2
0.005mol of polytetrahydrofuran diol is added into a four-neck flask provided with a thermometer and a condenser, vacuum pumping is carried out at 90 ℃ for half an hour for dehydration, the temperature is reduced to 70 ℃, 0.0195mol of isophorone diisocyanate and 0.1ml of dibutyltin dilaurate are added, and the reaction is carried out for 3 hours. Cooling to below 50 ℃, adding 10g of acetone to dilute the prepolymer, adding 0.01mol of N-methyldiethanolamine, and heating to 70 ℃ for reaction for 5 hours. Cooling to below 50 ℃, adding 5g of acetone, adding 0.01mol of glacial acetic acid at normal temperature, and reacting for half an hour. 35g of an aqueous solution containing an antibacterial agent was added dropwise from a constant pressure dropping funnel, and emulsification was performed at a high stirring rate. Stirring for 10 minutes, and removing acetone by rotary evaporation to obtain stable emulsion with the hydrophilic group content of 7.5 percent of the mass fraction of the polymer. Coating the emulsion on a polytetrafluoroethylene plate, and drying for 24h at 60 ℃ to obtain a polyurethane coating with the thickness of 0.3 mm.
Example 3
0.005mol of polytetrahydrofuran diol is added into a four-neck flask provided with a thermometer and a condenser, vacuum pumping is carried out at 90 ℃ for half an hour for dehydration, the temperature is reduced to 70 ℃, 0.013mol of isophorone diisocyanate and 0.1ml of dibutyltin dilaurate are added, and the reaction is carried out for 3 hours. Cooling to below 50 ℃, adding 10g of acetone to dilute the prepolymer, adding 0.005mol of N-methyldiethanolamine, and heating to 70 ℃ for reaction for 5 hours. Cooling to below 50 ℃, adding 5g of acetone, adding 0.005mol of glacial acetic acid at normal temperature, and reacting for half an hour. 35g of an aqueous solution containing an antibacterial agent was added dropwise from a constant pressure dropping funnel, and emulsification was performed at a high stirring rate. Stirring for 10 minutes, and removing acetone by rotary evaporation to obtain stable emulsion with the hydrophilic group content of 4.5 percent of the mass fraction of the polymer. Coating the emulsion on a polytetrafluoroethylene plate, and drying for 24h at 60 ℃ to obtain a polyurethane coating with the thickness of 0.3 mm.
Example 4
0.005mol of polytetrahydrofuran diol is added into a four-neck flask provided with a thermometer and a condenser, vacuum pumping is carried out at 90 ℃ for half an hour for dehydration, the temperature is reduced to 70 ℃, 0.00975mol of isophorone diisocyanate and 0.1ml of dibutyltin dilaurate are added, and the reaction is carried out for 3 hours. Cooling to below 50 ℃, adding 10g of acetone to dilute the prepolymer, adding 0.0025mol of N-methyldiethanolamine, and heating to 70 ℃ for reaction for 5 hours. Cooling to below 50 ℃, adding 5g of acetone, adding 0.0025mol of glacial acetic acid at normal temperature, and reacting for half an hour. 35g of an aqueous solution containing an antibacterial agent was added dropwise from a constant pressure dropping funnel, and emulsification was performed at a high stirring rate. Stirring for 10 minutes, and removing acetone by rotary evaporation to obtain emulsion with the hydrophilic group content of 2.4 percent of the mass fraction of the polymer. Coating the emulsion on a polytetrafluoroethylene plate, and drying for 24h at 60 ℃ to obtain a polyurethane coating with the thickness of 0.3 mm.
Example 5
0.005mol of polytetrahydrofuran diol is added into a four-neck flask provided with a thermometer and a condenser, vacuum pumping is carried out at 90 ℃ for half an hour for dehydration, the temperature is reduced to 70 ℃, 0.008125mol of isophorone diisocyanate and 0.1ml of dibutyltin dilaurate are added, and the reaction is carried out for 3 hours. Cooling to below 50 ℃, adding 10g of acetone to dilute the prepolymer, adding 0.00125mol of N-methyldiethanolamine, and heating to 70 ℃ to react for 5 hours. Cooling to below 50 ℃, adding 5g of acetone, adding 0.00125mol of glacial acetic acid at normal temperature, and reacting for half an hour. 35g of an aqueous solution containing an antibacterial agent was added dropwise from a constant pressure dropping funnel, and emulsification was performed at a high stirring rate. Stirring for 10 minutes, and removing acetone by rotary evaporation to obtain the polyurethane emulsion.
The hydrophilicity of the polyurethane prepared by the invention is mainly determined by the content of N-methyldiethanolamine in a molecular chain, and the higher the content of the N-methyldiethanolamine, the better the hydrophilicity of the molecular chain is, and the more uniform and stable the dispersion in water is. The higher the water absorption of the polyurethane film after film formation, the greater the degree of swelling in water. Tests show that the content of the hydrophilic groups in different hydrophilic polyurethanes in the examples is 1-10% of the mass of the polyurethane. The sample was cut into 2cmx2cm squares and placed in a vacuum oven at 60 ℃ for 24 hours. Weighing after taking out, and recording the mass as W0(ii) a Soaking in deionized water for 24 hr, taking out, sucking to dry the surface water, weighing and recording W1Water absorption of sample W1-W0/W0. With the increase of the content of the hydrophilic groups (1-10% of the mass of the polyurethane), the water absorption of the sample is from 5-25%. This results in a change in the swelling properties of the polyurethane itself, i.e., a different property of releasing the antimicrobial agent, as shown in FIG. 2.
And (3) drying the antibacterial coating, cutting the dried coating into round pieces with the diameter of 1mm, wherein the thickness is about 0.3mm, irradiating by ultraviolet rays for 3 hours, respectively placing the round pieces into culture media containing escherichia coli and staphylococcus aureus to perform antibacterial test, culturing the round pieces in a vibration table for 20 hours, and showing that an obvious inhibition zone appears around the sample, which indicates that the polyurethane coating has an inhibition effect on both the escherichia coli and the staphylococcus aureus, and the inhibition zone of the staphylococcus aureus is larger, so that the antibacterial coating has a better inhibition effect on the staphylococcus aureus. After the coating is formed into a film, the antibacterial agent is uniformly distributed in the coating, and the hydrophilic antibacterial agent is released to the surface of the coating when meeting water to kill bacteria. The antibacterial ability of the ionic water-based polyurethane is related to the hydrophilicity and hydrophobicity of a sample, the higher the quality of N-methyldiethanolamine contained in a molecular chain is, the better the hydrophilicity is, the more antibacterial agents are released to the surface from the interior of a coating, and even if the concentration of the surface antibacterial agent is lower, the better the antibacterial effect is, as shown in the attached figures 3 and 4, wherein the labels 1-5 in the figures correspond to the embodiments 1-5 respectively.
The polyurethane antibacterial coating prepared by the invention has good adhesive force with a PVC base material, the coating is coated on a PVC plate, a grid drawing test is carried out after drying, and a coating in a cutting area is intact, does not peel, does not stick up edges, and does not fall off, as shown in figure 5. The polyurethane antibacterial coating prepared by the invention has good mechanical properties after film forming, as shown in figure 1, and the yield strength reaches 0.7-0.76 MPa, the breaking strength reaches 0.4-0.5 MPa, and the breaking elongation reaches 270-275% through mechanical tests, which are determined by the structure of polyurethane. Polytetrahydrofuran diol provides flexibility for a molecular chain, isophorone diisocyanate and a small molecular chain extender provide rigidity for the molecular chain, and hydrogen bonds exist in the molecular chain, so that the strength of polyurethane is increased.
The preparation of the polyurethane antibacterial coating and the coating can be realized by adjusting the process parameters according to the content of the invention, and the performance basically consistent with the invention is shown. The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (10)
1. The method for improving the antibacterial performance of the polyurethane coating by using the hydrophilic chain extender is characterized by comprising the following steps:
step 1, uniformly mixing polytetrahydrofuran diol and isophorone diisocyanate, adding a catalyst, and reacting for 1-3 hours at 70-90 ℃, wherein the molar ratio of the polytetrahydrofuran diol to the isophorone diisocyanate is (5-10): (6-13);
step 2, reducing the system reacted in the step 1 to 45-50 ℃, diluting the prepolymer obtained in the step 1 by using acetone, adding N-methyldiethanolamine into the diluted system, and reacting at 50-70 ℃ for 1-5 hours, wherein the molar ratio of the N-methyldiethanolamine to the polytetrahydrofuran glycol is (2-30) to (5-10), and the amount of the acetone is 20-40% of the mass of the prepolymer;
step 3, cooling the system reacted in the step 2 to 40 +/-2 ℃, adding acetone for dilution, and then adding glacial acetic acid with the same mole as that of the N-methyldiethanolamine for neutralization, wherein the use amount of the acetone is 20-40% of the mass of the system reacted in the step 2;
and 4, dripping the water solution for dissolving and dispersing benzalkonium chloride into the system subjected to the reaction in the step 3 at a high rotating speed for emulsification, and removing acetone by rotary evaporation after the emulsification is finished to obtain the antibacterial waterborne polyurethane coating.
2. The method for improving the antibacterial property of the polyurethane coating by using the hydrophilic chain extender according to claim 1, wherein in the step 1, the polytetrahydrofuran polyether glycol is dehydrated in vacuum, and then protective gas is introduced, and isophorone diisocyanate is added and mixed uniformly to protect inert protective gas with odor, such as nitrogen, helium or argon.
3. The method for improving the antibacterial property of the polyurethane coating by using the hydrophilic chain extender according to claim 1, wherein in the step 1, the molar ratio of polytetrahydrofuran diol to isophorone diisocyanate is 5: (10-13) the catalyst is dibutyltin dilaurate, and the dosage is 0.05-0.1 volume part, and each volume part is 1 ml.
4. The method for improving the antibacterial property of the polyurethane coating by using the hydrophilic chain extender as claimed in claim 1, wherein in the step 1, the reaction is carried out at 80-90 ℃ for 2-3 hours.
5. The method for improving the antibacterial property of polyurethane coating by using hydrophilic chain extender as claimed in claim 1, wherein in step 2, the molar ratio of N-methyldiethanolamine to polytetrahydrofuran diol is (10-20) to (5-10), the amount of acetone is 30-40% of the mass of prepolymer, and the reaction is carried out at 50-60 ℃ for 3-5 hours.
6. The method for improving the antibacterial property of the polyurethane coating by using the hydrophilic chain extender as claimed in claim 1, wherein in the step 3, the amount of acetone is 30-40% of the mass of the system subjected to the reaction in the step 2.
7. The method for improving the antibacterial property of the polyurethane coating by using the hydrophilic chain extender is characterized in that in the step 3, the glacial acetic acid is added for neutralization for 30-60 min, preferably 40-50 min, and the pH of the system after the neutralization is 7 +/-0.2.
8. The method for improving the antibacterial property of the polyurethane coating by using the hydrophilic chain extender as claimed in claim 1, wherein in the step 4, the dosage of benzalkonium chloride is 0.1 of the mass of the system subjected to the reaction in the step 3, the high rotation speed is 800-.
9. The method for improving the antibacterial property of the polyurethane coating by using the hydrophilic chain extender as claimed in claim 1, wherein the temperature is controlled by using an oil bath, the temperature rising rate is 1-5 ℃/min, and the temperature lowering rate is 1-5 ℃/min.
10. The application of the hydrophilic chain extender N-methyldiethanolamine in adjusting the swelling degree of the polyurethane coating and/or the coating and the release capacity of the antibacterial agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811116530.7A CN110938359A (en) | 2018-09-25 | 2018-09-25 | Method for improving antibacterial property of polyurethane coating by using hydrophilic chain extender |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811116530.7A CN110938359A (en) | 2018-09-25 | 2018-09-25 | Method for improving antibacterial property of polyurethane coating by using hydrophilic chain extender |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110938359A true CN110938359A (en) | 2020-03-31 |
Family
ID=69904479
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811116530.7A Pending CN110938359A (en) | 2018-09-25 | 2018-09-25 | Method for improving antibacterial property of polyurethane coating by using hydrophilic chain extender |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110938359A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113563561A (en) * | 2021-08-10 | 2021-10-29 | 广东科力德新材料有限公司 | Resin for cathode electrophoretic coating color paste, preparation method of resin and coating color paste |
| CN113683880A (en) * | 2021-10-09 | 2021-11-23 | 厦门石破惊天材料科技有限公司 | Self-lubricating antibacterial hydrophilic TPU (thermoplastic polyurethane), preparation method and application thereof |
| CN114805743A (en) * | 2021-01-18 | 2022-07-29 | 万华化学集团股份有限公司 | Solvent-resistant waterborne polyurethane and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102272245A (en) * | 2008-12-01 | 2011-12-07 | 贝克顿·迪金森公司 | Antimicrobial UV curable coating compositions |
| CN103130976A (en) * | 2011-12-01 | 2013-06-05 | 孟宪清 | Waterborne polyurethane synthetic technology |
| CN103805046A (en) * | 2014-01-26 | 2014-05-21 | 陕西科技大学 | Graphene-containing waterborne polyurethane composite conductive coating prepared in situ and preparation method thereof |
| CN107129676A (en) * | 2017-06-15 | 2017-09-05 | 天津大学 | Cation aqueous polyurethane-chitosan blend thing and preparation method thereof |
-
2018
- 2018-09-25 CN CN201811116530.7A patent/CN110938359A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102272245A (en) * | 2008-12-01 | 2011-12-07 | 贝克顿·迪金森公司 | Antimicrobial UV curable coating compositions |
| CN103130976A (en) * | 2011-12-01 | 2013-06-05 | 孟宪清 | Waterborne polyurethane synthetic technology |
| CN103805046A (en) * | 2014-01-26 | 2014-05-21 | 陕西科技大学 | Graphene-containing waterborne polyurethane composite conductive coating prepared in situ and preparation method thereof |
| CN107129676A (en) * | 2017-06-15 | 2017-09-05 | 天津大学 | Cation aqueous polyurethane-chitosan blend thing and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114805743A (en) * | 2021-01-18 | 2022-07-29 | 万华化学集团股份有限公司 | Solvent-resistant waterborne polyurethane and preparation method thereof |
| CN114805743B (en) * | 2021-01-18 | 2024-02-02 | 万华化学集团股份有限公司 | Solvent-resistant waterborne polyurethane and preparation method thereof |
| CN113563561A (en) * | 2021-08-10 | 2021-10-29 | 广东科力德新材料有限公司 | Resin for cathode electrophoretic coating color paste, preparation method of resin and coating color paste |
| CN113683880A (en) * | 2021-10-09 | 2021-11-23 | 厦门石破惊天材料科技有限公司 | Self-lubricating antibacterial hydrophilic TPU (thermoplastic polyurethane), preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110938359A (en) | Method for improving antibacterial property of polyurethane coating by using hydrophilic chain extender | |
| EP2197930B1 (en) | Method for producing polyurethane foams | |
| CN111116859B (en) | Preparation method of antibacterial modified waterborne polyurethane | |
| Sahraro et al. | Guanidine hydrochloride embedded polyurethanes as antimicrobial and absorptive wound dressing membranes with promising cytocompatibility | |
| Wang et al. | IPN hydrogel nanocomposites based on agarose and ZnO with antifouling and bactericidal properties | |
| US20080306181A1 (en) | Antimicrobial polyurethane resins and products made therefrom | |
| JPH06104116B2 (en) | Wound dressing | |
| KR20090018608A (en) | Polyurethane foams for treating wounds | |
| BRPI0902711A2 (en) | medical device with a layer of antibacterial urea polyurethane | |
| DE102007048080A1 (en) | Biomedical foam products | |
| CN112500772B (en) | Betaine cation waterborne polyurethane antibacterial coating and preparation method thereof | |
| Zia et al. | Chitin based polyurethanes using hydroxyl terminated polybutadiene, part III: Surface characteristics | |
| EP2045279A1 (en) | Polyurethane foams for treating wounds | |
| Zhang et al. | Preparation and antibacterial properties of poly (hexamethylene guanidine hydrochloride) modified ionic waterborne polyurethane | |
| DE102007048078A1 (en) | Polyurethane foams for wound treatment | |
| CN110294828B (en) | Waterborne polyurethane and preparation method and application thereof | |
| KR20150098010A (en) | Antibacterial polyurethane foam dressing material and manufacturing method thereof | |
| Jia et al. | Synthesis and antibacterial investigation of cationic waterborne polyurethane containing siloxane | |
| CN109021550A (en) | A kind of hyperbranched aqueous polyurethane nano-zinc oxide composite material and preparation method thereof | |
| CN109134820B (en) | Anionic waterborne polyurethane nano zinc oxide composite material and preparation method thereof | |
| CN108070067A (en) | A kind of preparation method of Cross-linkable coating antibacterial polyurethane | |
| US20120308737A1 (en) | Method for antiseptic processing of the surface of a product made of silicone rubber material | |
| CN102100923B (en) | Preparation method of micron Ag2O2 doped chitosan hydrogel antibacterial auxiliary material | |
| CN114262455B (en) | Starch/epsilon-polylysine/poly (L-lactic acid) double-crosslinking material and preparation method and application thereof | |
| KR101924949B1 (en) | Environmentally friendly antimicrobial and mildew resistant synthetic fillers for artificial turf including antimicrobial polyurethane microcapsules and their preparation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200331 |
|
| RJ01 | Rejection of invention patent application after publication |