CN113402960A - Graphene oxide modified waterborne antibacterial polyurethane coating for woodware and preparation process - Google Patents
Graphene oxide modified waterborne antibacterial polyurethane coating for woodware and preparation process Download PDFInfo
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Abstract
The invention discloses a graphene oxide modified woodware water-based antibacterial polyurethane coating and a preparation process thereof, wherein the formula comprises the following components: the water-based polyurethane coating comprises water-based polyurethane, graphene oxide, a silane coupling agent, an organic synthetic monomer and an auxiliary agent, wherein the water-based polyurethane coating comprises the following components in parts by weight: 100 parts of waterborne polyurethane, 0.5-1.5 parts of graphene oxide, 0.25-0.75 part of silane coupling agent, 0.1-0.2 part of organic synthetic monomer and 0.1-0.5 part of auxiliary agent.
Description
Technical Field
The invention relates to the technical field of polyurethane coating production, in particular to a graphene oxide modified waterborne antibacterial polyurethane coating for woodware and a preparation process thereof.
Background
The polyurethane coating is a common coating, the classification of the polyurethane coating is more, the waterborne polyurethane coating is an important component of the waterborne polyurethane coating, and the waterborne polyurethane has the excellent performances of easy modification, difficult damage, strong surface coverage, low-temperature film formation, environmental protection and the like, but compared with the traditional solvent-based coating, the waterborne polyurethane coating has poor dispersion stability against strong mechanical acting force and inferior mechanical property to the solvent-based coating, so a new process is needed for improving the waterborne polyurethane coating.
The existing waterborne polyurethane coating on the market and the preparation process thereof are many, and can basically meet the use requirements of people, but certain defects still exist, and the specific problems are as follows.
(1) In the existing waterborne polyurethane coating and the preparation process, graphene oxide is used as a modifier to change the performance of the waterborne polyurethane coating, but the graphene oxide directly used as the modifier can damage the stability of the polyurethane emulsion, and the modified waterborne polyurethane coating has poor antibacterial property;
(2) the existing preparation process of the waterborne polyurethane coating is simple, has no fixed process standard, and is difficult to find out the optimal process scheme;
(3) the existing waterborne polyurethane coating is not sufficiently stirred in the preparation process, so that the problems of ion deposition and uneven distribution of various materials are easily caused, and the service performance of the waterborne polyurethane coating is greatly reduced.
Disclosure of Invention
The invention aims to provide a graphene oxide modified woodware water-based antibacterial polyurethane coating and a preparation process thereof, and aims to solve the problems of poor antibacterial property, uneven process standard level and ion deposition in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme: the graphene oxide modified waterborne antibacterial polyurethane coating for woodware comprises the following components in percentage by weight: the water-based polyurethane coating comprises water-based polyurethane, graphene oxide, a silane coupling agent, an organic synthetic monomer and an auxiliary agent, wherein the water-based polyurethane coating comprises the following components in parts by weight: 100 parts of waterborne polyurethane, 0.5-1.5 parts of graphene oxide, 0.25-0.75 part of silane coupling agent, 0.1-0.2 part of organic synthetic monomer and 0.1-0.5 part of auxiliary agent.
Preferably, the aqueous polyurethane is one of cationic aqueous polyurethane and anionic aqueous polyurethane.
Preferably, the auxiliary agent is a curing agent and a defoaming agent.
Preferably, the organic synthetic monomer is an acrylate monomer.
The preparation process of the graphene oxide modified waterborne antibacterial polyurethane coating for woodware comprises the following steps of firstly, weighing raw materials; step two, mixing for the first time; step three, ultrasonic dispersion; modifying graphene oxide; step five, mixing for the second time; step six, coating the coating;
in the first step, 100 parts of waterborne polyurethane, 0.5-1.5 parts of graphene oxide, 0.25-0.75 parts of silane coupling agent, 0.1-0.2 parts of organic synthetic monomer and 0.1-0.5 parts of auxiliary agent are respectively weighed according to the parts by weight of the components;
in the second step, adding the graphene oxide weighed in the first step into a proper amount of ethanol solution, then carrying out magnetic stirring, and uniformly stirring to obtain a graphene oxide solution semi-finished product for later use;
in the third step, the graphene oxide solution semi-finished product prepared in the second step is subjected to ultrasonic dispersion by using an ultrasonic generator to prepare a uniformly dispersed graphene oxide solution finished product for later use;
adding the graphene oxide solution finished product prepared in the step three into a stirrer, then adding the silane coupling agent and the organic synthetic monomer weighed in the step one while stirring, stirring for 30-60min, putting the mixture into a water bath kettle for water bath for 6-8h after stirring is finished, carrying out suction filtration on the reactant for 3-5 times after the water bath is finished, then cleaning the product obtained by suction filtration, and carrying out vacuum drying to obtain modified graphene oxide for later use;
adding the waterborne polyurethane weighed in the step one into a high-shear emulsifying machine, then adding the modified graphene oxide prepared in the step four, carrying out first emulsification shearing, adding the auxiliary agent weighed in the step one after the full emulsification shearing is finished, carrying out second emulsification shearing, and uniformly mixing to obtain the graphene oxide modified woodware waterborne antibacterial polyurethane coating;
and in the sixth step, the graphene oxide modified woodware waterborne antibacterial polyurethane coating prepared in the fifth step is coated on woodware, then is cured at normal temperature for 5-7 hours, and then is dried in a drying oven.
Preferably, in the second step, the magnetic stirring time is 15-20 min.
Preferably, in the third step, the time for ultrasonic dispersion is 10-15 min.
Preferably, in the fourth step, the stirring speed is 600-800r/min, the vacuum drying temperature is 70-90 ℃, and the drying time is 4-7 h.
Preferably, in the fifth step, the rotation speed of the first emulsification shearing is 700-700 r/min, the emulsification shearing time is 40-60min, the rotation speed of the second emulsification shearing is 300-400r/min, and the emulsification shearing time is 40-60 min.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, the graphene oxide is modified by the silane coupling agent and the organic synthetic monomer, so that the compatibility of the graphene oxide in organic matters is improved, the reaction activity of the graphene oxide is improved, and then the modified graphene oxide is utilized to synthesize the waterborne polyurethane coating, which is beneficial to improving the antibacterial performance of the coating;
2. according to the invention, through magnetic stirring and ultrasonic dispersion, the graphene oxide is uniformly dispersed, and through twice stirring and mixing of the stirrer and the high-shear emulsifier, the components are fully and uniformly mixed, the occurrence of ion deposition is avoided, and the product quality is favorably improved;
3. the method has the advantages of simple process and standard flow parameters, and the performance of the coating is researched by changing the curing time, the addition amount of the graphene oxide and the type of polyurethane, so that the method is favorable for obtaining the optimal process.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1, the present invention provides a technical solution:
example 1:
the graphene oxide modified waterborne antibacterial polyurethane coating for woodware comprises the following components in percentage by weight: the water-based polyurethane coating comprises water-based polyurethane, graphene oxide, a silane coupling agent, an organic synthetic monomer and an auxiliary agent, wherein the water-based polyurethane coating comprises the following components in parts by weight: 100 parts of waterborne polyurethane, 0.5-1.5 parts of graphene oxide, 0.25-0.75 part of silane coupling agent, 0.1-0.2 part of organic synthetic monomer and 0.1-0.5 part of auxiliary agent, wherein the waterborne polyurethane is one of cationic waterborne polyurethane and anionic waterborne polyurethane, the auxiliary agent is a curing agent and a defoaming agent, and the organic synthetic monomer is an acrylate monomer.
The preparation process of the graphene oxide modified waterborne antibacterial polyurethane coating for woodware comprises the following steps of firstly, weighing raw materials; step two, mixing for the first time; step three, ultrasonic dispersion; modifying graphene oxide; step five, mixing for the second time; step six, coating the coating;
in the first step, 100 parts of cationic waterborne polyurethane, 0.5 part of graphene oxide, 0.25 part of silane coupling agent, 0.1 part of organic synthetic monomer and 0.1 part of auxiliary agent are weighed according to the parts by weight of the components;
in the second step, adding the graphene oxide weighed in the first step into a proper amount of ethanol solution, then carrying out magnetic stirring for 15-20min, and uniformly stirring to obtain a graphene oxide solution semi-finished product for later use;
in the third step, the semi-finished product of the graphene oxide solution prepared in the second step is subjected to ultrasonic dispersion by using an ultrasonic generator, the ultrasonic dispersion time is 10-15min, and the uniformly dispersed finished product of the graphene oxide solution is prepared for later use;
adding the graphene oxide solution finished product prepared in the step three into a stirrer, then adding the silane coupling agent and the organic synthetic monomer weighed in the step one while stirring, stirring for 30-60min, putting the mixture into a water bath kettle after stirring for 6-8h, carrying out suction filtration on a reactant for 3-5 times after the water bath is finished, cleaning a product obtained by suction filtration, and carrying out vacuum drying at the temperature of 70-90 ℃ for later use, wherein the stirring speed is 800r/min, the vacuum drying temperature is 70-90 ℃, and the drying time is 4-7 h;
adding the cationic waterborne polyurethane weighed in the step one into a high-shear emulsifying machine, then adding the modified graphene oxide prepared in the step four, carrying out first emulsification shearing, adding the auxiliary agent weighed in the step one after the full emulsification shearing is finished, carrying out second emulsification shearing, and uniformly mixing to obtain the graphene oxide modified woodware waterborne antibacterial polyurethane coating, wherein the rotating speed of the first emulsification shearing is 700 DEG/min, the emulsification shearing time is 40-60min, the rotating speed of the second emulsification shearing is 300 DEG/min, and the emulsification shearing time is 40-60 min;
and in the sixth step, the graphene oxide modified woodware waterborne antibacterial polyurethane coating prepared in the fifth step is coated on woodware, then is cured at normal temperature for 5-7 hours, and then is dried in a drying oven.
Comparative example 1:
the graphene oxide modified waterborne antibacterial polyurethane coating for woodware comprises the following components in percentage by weight: the water-based polyurethane coating comprises water-based polyurethane, graphene oxide, a silane coupling agent, an organic synthetic monomer and an auxiliary agent, wherein the water-based polyurethane coating comprises the following components in parts by weight: 100 parts of waterborne polyurethane, 0.5-1.5 parts of graphene oxide, 0.25-0.75 part of silane coupling agent, 0.1-0.2 part of organic synthetic monomer and 0.1-0.5 part of auxiliary agent, wherein the waterborne polyurethane is one of cationic waterborne polyurethane and anionic waterborne polyurethane, the auxiliary agent is a curing agent and a defoaming agent, and the organic synthetic monomer is an acrylate monomer.
The preparation process of the graphene oxide modified waterborne antibacterial polyurethane coating for woodware comprises the following steps of firstly, weighing raw materials; step two, mixing for the first time; step three, ultrasonic dispersion; modifying graphene oxide; step five, mixing for the second time; step six, coating the coating;
in the first step, 100 parts of anionic polyurethane, 0.5 part of graphene oxide, 0.25 part of silane coupling agent, 0.1 part of organic synthetic monomer and 0.1 part of auxiliary agent are weighed according to the parts by weight of the components;
in the second step, adding the graphene oxide weighed in the first step into a proper amount of ethanol solution, then carrying out magnetic stirring for 15-20min, and uniformly stirring to obtain a graphene oxide solution semi-finished product for later use;
in the third step, the semi-finished product of the graphene oxide solution prepared in the second step is subjected to ultrasonic dispersion by using an ultrasonic generator, the ultrasonic dispersion time is 10-15min, and the uniformly dispersed finished product of the graphene oxide solution is prepared for later use;
adding the graphene oxide solution finished product prepared in the step three into a stirrer, then adding the silane coupling agent and the organic synthetic monomer weighed in the step one while stirring, stirring for 30-60min, putting the mixture into a water bath kettle after stirring for 6-8h, carrying out suction filtration on a reactant for 3-5 times after the water bath is finished, cleaning a product obtained by suction filtration, and carrying out vacuum drying at the temperature of 70-90 ℃ for later use, wherein the stirring speed is 800r/min, the vacuum drying temperature is 70-90 ℃, and the drying time is 4-7 h;
adding the anionic waterborne polyurethane weighed in the step one into a high-shear emulsifying machine, then adding the modified graphene oxide prepared in the step four, performing first emulsification shearing, adding the auxiliary weighed in the step one after the full emulsification shearing is completed, performing second emulsification shearing, and uniformly mixing to obtain the graphene oxide modified waterborne antibacterial polyurethane coating for the woodware, wherein the rotating speed of the first emulsification shearing is 500-700r/min, the emulsification shearing time is 40-60min, the rotating speed of the second emulsification shearing is 300-400r/min, and the emulsification shearing time is 40-60 min;
and in the sixth step, the graphene oxide modified woodware waterborne antibacterial polyurethane coating prepared in the fifth step is coated on woodware, then is cured at normal temperature for 5-7 hours, and then is dried in a drying oven.
The cured wood articles obtained from the above examples and comparative examples were compared and the results are shown in the following table:
the brightness of the graphene oxide modified woodenware aqueous antibacterial polyurethane coating prepared by adopting cationic aqueous polyurethane as a raw material is obviously superior to that prepared by adopting anionic aqueous polyurethane as a raw material.
Example 2:
the graphene oxide modified waterborne antibacterial polyurethane coating for woodware comprises the following components in percentage by weight: the water-based polyurethane coating comprises water-based polyurethane, graphene oxide, a silane coupling agent, an organic synthetic monomer and an auxiliary agent, wherein the water-based polyurethane coating comprises the following components in parts by weight: 100 parts of waterborne polyurethane, 0.5-1.5 parts of graphene oxide, 0.25-0.75 part of silane coupling agent, 0.1-0.2 part of organic synthetic monomer and 0.1-0.5 part of auxiliary agent, wherein the waterborne polyurethane is one or a mixture of cationic waterborne polyurethane and anionic waterborne polyurethane, the auxiliary agent is a curing agent and a defoaming agent, and the organic synthetic monomer is an acrylate monomer.
The preparation process of the graphene oxide modified waterborne antibacterial polyurethane coating for woodware comprises the following steps of firstly, weighing raw materials; step two, mixing for the first time; step three, ultrasonic dispersion; modifying graphene oxide; step five, mixing for the second time; step six, coating the coating;
in the first step, 100 parts of cationic waterborne polyurethane, 0.5 part of graphene oxide, 0.25 part of silane coupling agent, 0.1 part of organic synthetic monomer and 0.1 part of auxiliary agent are weighed according to the parts by weight of the components;
in the second step, adding the graphene oxide weighed in the first step into a proper amount of ethanol solution, then carrying out magnetic stirring for 15-20min, and uniformly stirring to obtain a graphene oxide solution semi-finished product for later use;
in the third step, the semi-finished product of the graphene oxide solution prepared in the second step is subjected to ultrasonic dispersion by using an ultrasonic generator, the ultrasonic dispersion time is 10-15min, and the uniformly dispersed finished product of the graphene oxide solution is prepared for later use;
adding the graphene oxide solution finished product prepared in the step three into a stirrer, then adding the silane coupling agent and the organic synthetic monomer weighed in the step one while stirring, stirring for 30-60min, putting the mixture into a water bath kettle after stirring for 6-8h, carrying out suction filtration on a reactant for 3-5 times after the water bath is finished, cleaning a product obtained by suction filtration, and carrying out vacuum drying at the temperature of 70-90 ℃ for later use, wherein the stirring speed is 800r/min, the vacuum drying temperature is 70-90 ℃, and the drying time is 4-7 h;
adding the cationic waterborne polyurethane weighed in the step one into a high-shear emulsifying machine, then adding the modified graphene oxide prepared in the step four, carrying out first emulsification shearing, adding the auxiliary agent weighed in the step one after the full emulsification shearing is finished, carrying out second emulsification shearing, and uniformly mixing to obtain the graphene oxide modified woodware waterborne antibacterial polyurethane coating, wherein the rotating speed of the first emulsification shearing is 700 DEG/min, the emulsification shearing time is 40-60min, the rotating speed of the second emulsification shearing is 300 DEG/min, and the emulsification shearing time is 40-60 min;
and in the sixth step, the graphene oxide modified woodware waterborne antibacterial polyurethane coating prepared in the fifth step is coated on woodware, then is cured at normal temperature for 5-7 hours, and then is dried in a drying oven.
Comparative example 2:
the graphene oxide modified waterborne antibacterial polyurethane coating for woodware comprises the following components in percentage by weight: the water-based polyurethane coating comprises water-based polyurethane, graphene oxide, a silane coupling agent, an organic synthetic monomer and an auxiliary agent, wherein the water-based polyurethane coating comprises the following components in parts by weight: 100 parts of waterborne polyurethane, 0.5-1.5 parts of graphene oxide, 0.25-0.75 part of silane coupling agent, 0.1-0.2 part of organic synthetic monomer and 0.1-0.5 part of auxiliary agent, wherein the waterborne polyurethane is one or a mixture of cationic waterborne polyurethane and anionic waterborne polyurethane, the auxiliary agent is a curing agent and a defoaming agent, and the organic synthetic monomer is an acrylate monomer.
The preparation process of the graphene oxide modified waterborne antibacterial polyurethane coating for woodware comprises the following steps of firstly, weighing raw materials; step two, mixing for the first time; step three, ultrasonic dispersion; modifying graphene oxide; step five, mixing for the second time; step six, coating the coating;
in the first step, 100 parts of cationic waterborne polyurethane, 0.3 part of graphene oxide, 0.25 part of silane coupling agent, 0.1 part of organic synthetic monomer and 0.1 part of auxiliary agent are weighed according to the parts by weight of the components;
in the second step, adding the graphene oxide weighed in the first step into a proper amount of ethanol solution, then carrying out magnetic stirring for 15-20min, and uniformly stirring to obtain a graphene oxide solution semi-finished product for later use;
in the third step, the semi-finished product of the graphene oxide solution prepared in the second step is subjected to ultrasonic dispersion by using an ultrasonic generator, the ultrasonic dispersion time is 10-15min, and the uniformly dispersed finished product of the graphene oxide solution is prepared for later use;
adding the graphene oxide solution finished product prepared in the step three into a stirrer, then adding the silane coupling agent and the organic synthetic monomer weighed in the step one while stirring, stirring for 30-60min, putting the mixture into a water bath kettle after stirring for 6-8h, carrying out suction filtration on a reactant for 3-5 times after the water bath is finished, cleaning a product obtained by suction filtration, and carrying out vacuum drying at the temperature of 70-90 ℃ for later use, wherein the stirring speed is 800r/min, the vacuum drying temperature is 70-90 ℃, and the drying time is 4-7 h;
adding the cationic waterborne polyurethane weighed in the step one into a high-shear emulsifying machine, then adding the modified graphene oxide prepared in the step four, carrying out first emulsification shearing, adding the auxiliary agent weighed in the step one after the full emulsification shearing is finished, carrying out second emulsification shearing, and uniformly mixing to obtain the graphene oxide modified woodware waterborne antibacterial polyurethane coating, wherein the rotating speed of the first emulsification shearing is 700 DEG/min, the emulsification shearing time is 40-60min, the rotating speed of the second emulsification shearing is 300 DEG/min, and the emulsification shearing time is 40-60 min;
and in the sixth step, the graphene oxide modified woodware waterborne antibacterial polyurethane coating prepared in the fifth step is coated on woodware, then is cured at normal temperature for 5-7 hours, and then is dried in a drying oven.
Comparative example 3:
the graphene oxide modified waterborne antibacterial polyurethane coating for woodware comprises the following components in percentage by weight: the water-based polyurethane coating comprises water-based polyurethane, graphene oxide, a silane coupling agent, an organic synthetic monomer and an auxiliary agent, wherein the water-based polyurethane coating comprises the following components in parts by weight: 100 parts of waterborne polyurethane, 0.5-1.5 parts of graphene oxide, 0.25-0.75 part of silane coupling agent, 0.1-0.2 part of organic synthetic monomer and 0.1-0.5 part of auxiliary agent, wherein the waterborne polyurethane is one or a mixture of cationic waterborne polyurethane and anionic waterborne polyurethane, the auxiliary agent is a curing agent and a defoaming agent, and the organic synthetic monomer is an acrylate monomer.
The preparation process of the graphene oxide modified waterborne antibacterial polyurethane coating for woodware comprises the following steps of firstly, weighing raw materials; step two, mixing for the first time; step three, ultrasonic dispersion; modifying graphene oxide; step five, mixing for the second time; step six, coating the coating;
in the first step, 100 parts of cationic waterborne polyurethane, 1.8 parts of graphene oxide, 0.25 part of silane coupling agent, 0.1 part of organic synthetic monomer and 0.1 part of auxiliary agent are weighed according to the parts by weight of the components;
in the second step, adding the graphene oxide weighed in the first step into a proper amount of ethanol solution, then carrying out magnetic stirring for 15-20min, and uniformly stirring to obtain a graphene oxide solution semi-finished product for later use;
in the third step, the semi-finished product of the graphene oxide solution prepared in the second step is subjected to ultrasonic dispersion by using an ultrasonic generator, the ultrasonic dispersion time is 10-15min, and the uniformly dispersed finished product of the graphene oxide solution is prepared for later use;
adding the graphene oxide solution finished product prepared in the step three into a stirrer, then adding the silane coupling agent and the organic synthetic monomer weighed in the step one while stirring, stirring for 30-60min, putting the mixture into a water bath kettle after stirring for 6-8h, carrying out suction filtration on a reactant for 3-5 times after the water bath is finished, cleaning a product obtained by suction filtration, and carrying out vacuum drying at the temperature of 70-90 ℃ for later use, wherein the stirring speed is 800r/min, the vacuum drying temperature is 70-90 ℃, and the drying time is 4-7 h;
adding the cationic waterborne polyurethane weighed in the step one into a high-shear emulsifying machine, then adding the modified graphene oxide prepared in the step four, carrying out first emulsification shearing, adding the auxiliary agent weighed in the step one after the full emulsification shearing is finished, carrying out second emulsification shearing, and uniformly mixing to obtain the graphene oxide modified woodware waterborne antibacterial polyurethane coating, wherein the rotating speed of the first emulsification shearing is 700 DEG/min, the emulsification shearing time is 40-60min, the rotating speed of the second emulsification shearing is 300 DEG/min, and the emulsification shearing time is 40-60 min;
and in the sixth step, the graphene oxide modified woodware waterborne antibacterial polyurethane coating prepared in the fifth step is coated on woodware, then is cured at normal temperature for 5-7 hours, and then is dried in a drying oven.
The cured woodware obtained in the above examples and comparative examples is put into a specific test box, the saline water containing 4.5-5.5% of sodium chloride and having a pH value of 6.5-7.2 is sprayed by a spraying device, the salt mist is settled on a test piece to be tested, the surface corrosion state of the test piece is observed after a certain period of time, and the results are compared as follows:
when the addition amount of the graphene oxide is between 0.5 and 1.5 parts, the bonding degree of the coating on the woodware is the best.
Example 3:
the graphene oxide modified waterborne antibacterial polyurethane coating for woodware comprises the following components in percentage by weight: the water-based polyurethane coating comprises water-based polyurethane, graphene oxide, a silane coupling agent, an organic synthetic monomer and an auxiliary agent, wherein the water-based polyurethane coating comprises the following components in parts by weight: 100 parts of waterborne polyurethane, 0.5-1.5 parts of graphene oxide, 0.25-0.75 part of silane coupling agent, 0.1-0.2 part of organic synthetic monomer and 0.1-0.5 part of auxiliary agent, wherein the waterborne polyurethane is one or a mixture of cationic waterborne polyurethane and anionic waterborne polyurethane, the auxiliary agent is a curing agent and a defoaming agent, and the organic synthetic monomer is an acrylate monomer.
The preparation process of the graphene oxide modified waterborne antibacterial polyurethane coating for woodware comprises the following steps of firstly, weighing raw materials; step two, mixing for the first time; step three, ultrasonic dispersion; modifying graphene oxide; step five, mixing for the second time; step six, coating the coating;
in the first step, 100 parts of cationic waterborne polyurethane, 0.5 part of graphene oxide, 0.25 part of silane coupling agent, 0.1 part of organic synthetic monomer and 0.1 part of auxiliary agent are weighed according to the parts by weight of the components;
in the second step, adding the graphene oxide weighed in the first step into a proper amount of ethanol solution, then carrying out magnetic stirring for 15-20min, and uniformly stirring to obtain a graphene oxide solution semi-finished product for later use;
in the third step, the semi-finished product of the graphene oxide solution prepared in the second step is subjected to ultrasonic dispersion by using an ultrasonic generator, the ultrasonic dispersion time is 10-15min, and the uniformly dispersed finished product of the graphene oxide solution is prepared for later use;
adding the graphene oxide solution finished product prepared in the step three into a stirrer, then adding the silane coupling agent and the organic synthetic monomer weighed in the step one while stirring, stirring for 30-60min, putting the mixture into a water bath kettle after stirring for 6-8h, carrying out suction filtration on a reactant for 3-5 times after the water bath is finished, cleaning a product obtained by suction filtration, and carrying out vacuum drying at the temperature of 70-90 ℃ for later use, wherein the stirring speed is 800r/min, the vacuum drying temperature is 70-90 ℃, and the drying time is 4-7 h;
adding the cationic waterborne polyurethane weighed in the step one into a high-shear emulsifying machine, then adding the modified graphene oxide prepared in the step four, carrying out first emulsification shearing, adding the auxiliary agent weighed in the step one after the full emulsification shearing is finished, carrying out second emulsification shearing, and uniformly mixing to obtain the graphene oxide modified woodware waterborne antibacterial polyurethane coating, wherein the rotating speed of the first emulsification shearing is 700 DEG/min, the emulsification shearing time is 40-60min, the rotating speed of the second emulsification shearing is 300 DEG/min, and the emulsification shearing time is 40-60 min;
and in the sixth step, the graphene oxide modified woodware waterborne antibacterial polyurethane coating prepared in the fifth step is coated on woodware, then is cured at normal temperature for 6 hours, and then is dried in a drying oven.
Comparative example 4:
the graphene oxide modified waterborne antibacterial polyurethane coating for woodware comprises the following components in percentage by weight: the water-based polyurethane coating comprises water-based polyurethane, graphene oxide, a silane coupling agent, an organic synthetic monomer and an auxiliary agent, wherein the water-based polyurethane coating comprises the following components in parts by weight: 100 parts of waterborne polyurethane, 0.5-1.5 parts of graphene oxide, 0.25-0.75 part of silane coupling agent, 0.1-0.2 part of organic synthetic monomer and 0.1-0.5 part of auxiliary agent, wherein the waterborne polyurethane is one or a mixture of cationic waterborne polyurethane and anionic waterborne polyurethane, the auxiliary agent is a curing agent and a defoaming agent, and the organic synthetic monomer is an acrylate monomer.
The preparation process of the graphene oxide modified waterborne antibacterial polyurethane coating for woodware comprises the following steps of firstly, weighing raw materials; step two, mixing for the first time; step three, ultrasonic dispersion; modifying graphene oxide; step five, mixing for the second time; step six, coating the coating;
in the first step, 100 parts of cationic waterborne polyurethane, 0.5 part of graphene oxide, 0.25 part of silane coupling agent, 0.1 part of organic synthetic monomer and 0.1 part of auxiliary agent are weighed according to the parts by weight of the components;
in the second step, adding the graphene oxide weighed in the first step into a proper amount of ethanol solution, then carrying out magnetic stirring for 15-20min, and uniformly stirring to obtain a graphene oxide solution semi-finished product for later use;
in the third step, the semi-finished product of the graphene oxide solution prepared in the second step is subjected to ultrasonic dispersion by using an ultrasonic generator, the ultrasonic dispersion time is 10-15min, and the uniformly dispersed finished product of the graphene oxide solution is prepared for later use;
adding the graphene oxide solution finished product prepared in the step three into a stirrer, then adding the silane coupling agent and the organic synthetic monomer weighed in the step one while stirring, stirring for 30-60min, putting the mixture into a water bath kettle after stirring for 6-8h, carrying out suction filtration on a reactant for 3-5 times after the water bath is finished, cleaning a product obtained by suction filtration, and carrying out vacuum drying at the temperature of 70-90 ℃ for later use, wherein the stirring speed is 800r/min, the vacuum drying temperature is 70-90 ℃, and the drying time is 4-7 h;
adding the cationic waterborne polyurethane weighed in the step one into a high-shear emulsifying machine, then adding the modified graphene oxide prepared in the step four, carrying out first emulsification shearing, adding the auxiliary agent weighed in the step one after the full emulsification shearing is finished, carrying out second emulsification shearing, and uniformly mixing to obtain the graphene oxide modified woodware waterborne antibacterial polyurethane coating, wherein the rotating speed of the first emulsification shearing is 700 DEG/min, the emulsification shearing time is 40-60min, the rotating speed of the second emulsification shearing is 300 DEG/min, and the emulsification shearing time is 40-60 min;
and in the sixth step, the graphene oxide modified woodware waterborne antibacterial polyurethane coating prepared in the fifth step is coated on woodware, then is cured at normal temperature for 3 hours, and then is dried in a drying oven.
Comparative example 5:
the graphene oxide modified waterborne antibacterial polyurethane coating for woodware comprises the following components in percentage by weight: the water-based polyurethane coating comprises water-based polyurethane, graphene oxide, a silane coupling agent, an organic synthetic monomer and an auxiliary agent, wherein the water-based polyurethane coating comprises the following components in parts by weight: 100 parts of waterborne polyurethane, 0.5-1.5 parts of graphene oxide, 0.25-0.75 part of silane coupling agent, 0.1-0.2 part of organic synthetic monomer and 0.1-0.5 part of auxiliary agent, wherein the waterborne polyurethane is one or a mixture of cationic waterborne polyurethane and anionic waterborne polyurethane, the auxiliary agent is a curing agent and a defoaming agent, and the organic synthetic monomer is an acrylate monomer.
The preparation process of the graphene oxide modified waterborne antibacterial polyurethane coating for woodware comprises the following steps of firstly, weighing raw materials; step two, mixing for the first time; step three, ultrasonic dispersion; modifying graphene oxide; step five, mixing for the second time; step six, coating the coating;
in the first step, 100 parts of cationic waterborne polyurethane, 0.5 part of graphene oxide, 0.25 part of silane coupling agent, 0.1 part of organic synthetic monomer and 0.1 part of auxiliary agent are weighed according to the parts by weight of the components;
in the second step, adding the graphene oxide weighed in the first step into a proper amount of ethanol solution, then carrying out magnetic stirring for 15-20min, and uniformly stirring to obtain a graphene oxide solution semi-finished product for later use;
in the third step, the semi-finished product of the graphene oxide solution prepared in the second step is subjected to ultrasonic dispersion by using an ultrasonic generator, the ultrasonic dispersion time is 10-15min, and the uniformly dispersed finished product of the graphene oxide solution is prepared for later use;
adding the graphene oxide solution finished product prepared in the step three into a stirrer, then adding the silane coupling agent and the organic synthetic monomer weighed in the step one while stirring, stirring for 30-60min, putting the mixture into a water bath kettle after stirring for 6-8h, carrying out suction filtration on a reactant for 3-5 times after the water bath is finished, cleaning a product obtained by suction filtration, and carrying out vacuum drying at the temperature of 70-90 ℃ for later use, wherein the stirring speed is 800r/min, the vacuum drying temperature is 70-90 ℃, and the drying time is 4-7 h;
adding the cationic waterborne polyurethane weighed in the step one into a high-shear emulsifying machine, then adding the modified graphene oxide prepared in the step four, carrying out first emulsification shearing, adding the auxiliary agent weighed in the step one after the full emulsification shearing is finished, carrying out second emulsification shearing, and uniformly mixing to obtain the graphene oxide modified woodware waterborne antibacterial polyurethane coating, wherein the rotating speed of the first emulsification shearing is 700 DEG/min, the emulsification shearing time is 40-60min, the rotating speed of the second emulsification shearing is 300 DEG/min, and the emulsification shearing time is 40-60 min;
and in the sixth step, the graphene oxide modified woodware waterborne antibacterial polyurethane coating prepared in the fifth step is coated on woodware, then is cured at normal temperature for 10 hours, and then is dried in a drying oven.
The cured woodware obtained in the above examples and comparative examples is put into a specific test box, the saline water containing 4.5-5.5% of sodium chloride and having a pH value of 6.5-7.2 is sprayed by a spraying device, the salt mist is settled on a test piece to be tested, the surface corrosion state of the test piece is observed after a certain period of time, and the results are compared as follows:
the curing time is between 5 and 7 hours, and the curing effect is best.
Compared with the prior art, the invention has the following beneficial effects: the invention modifies the graphene oxide by the silane coupling agent and the organic synthetic monomer, improves the compatibility of the graphene oxide in organic matters, improves the reaction activity of the graphene oxide, then the modified graphene oxide is utilized to synthesize the waterborne polyurethane coating, which is beneficial to improving the antibacterial property of the coating, through the combined action of magnetic stirring, ultrasonic dispersion, a stirrer and a high-shear emulsifier, the components are favorably and fully mixed, the occurrence of ion deposition is avoided, meanwhile, the influence of curing time, graphene oxide addition amount, different types of polyurethane and the like on the performance of the coating is researched through a neutral salt spray test analysis technology, so that an optimal process is obtained, the cationic waterborne polyurethane is adopted as a formula, the curing time is 5-7h, and the addition amount of the graphene oxide is 0.5-1.5 parts.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. The graphene oxide modified waterborne antibacterial polyurethane coating for woodware comprises the following components in percentage by weight: waterborne polyurethane, graphene oxide, a silane coupling agent, an organic synthetic monomer and an auxiliary agent, and is characterized in that: the weight parts of the components are respectively as follows: 100 parts of waterborne polyurethane, 0.5-1.5 parts of graphene oxide, 0.25-0.75 part of silane coupling agent, 0.1-0.2 part of organic synthetic monomer and 0.1-0.5 part of auxiliary agent.
2. The graphene oxide modified waterborne antibacterial polyurethane coating for woodware according to claim 1, characterized in that: the waterborne polyurethane is one of cationic waterborne polyurethane and anionic waterborne polyurethane.
3. The graphene oxide modified waterborne antibacterial polyurethane coating for woodware according to claim 1, characterized in that: the auxiliary agent is a curing agent and a defoaming agent.
4. The graphene oxide modified waterborne antibacterial polyurethane coating for woodware according to claim 1, characterized in that: the organic synthetic monomer is an acrylate monomer.
5. The preparation process of the graphene oxide modified waterborne antibacterial polyurethane coating for woodware comprises the following steps of firstly, weighing raw materials; step two, mixing for the first time; step three, ultrasonic dispersion; modifying graphene oxide; step five, mixing for the second time; step six, coating the coating; the method is characterized in that:
in the first step, 100 parts of waterborne polyurethane, 0.5-1.5 parts of graphene oxide, 0.25-0.75 parts of silane coupling agent, 0.1-0.2 parts of organic synthetic monomer and 0.1-0.5 parts of auxiliary agent are respectively weighed according to the parts by weight of the components;
in the second step, adding the graphene oxide weighed in the first step into a proper amount of ethanol solution, then carrying out magnetic stirring, and uniformly stirring to obtain a graphene oxide solution semi-finished product for later use;
in the third step, the graphene oxide solution semi-finished product prepared in the second step is subjected to ultrasonic dispersion by using an ultrasonic generator to prepare a uniformly dispersed graphene oxide solution finished product for later use;
adding the graphene oxide solution finished product prepared in the step three into a stirrer, then adding the silane coupling agent and the organic synthetic monomer weighed in the step one while stirring, stirring for 30-60min, putting the mixture into a water bath kettle for water bath for 6-8h after stirring is finished, carrying out suction filtration on the reactant for 3-5 times after the water bath is finished, then cleaning the product obtained by suction filtration, and carrying out vacuum drying to obtain modified graphene oxide for later use;
adding the waterborne polyurethane weighed in the step one into a high-shear emulsifying machine, then adding the modified graphene oxide prepared in the step four, carrying out first emulsification shearing, adding the auxiliary agent weighed in the step one after the full emulsification shearing is finished, carrying out second emulsification shearing, and uniformly mixing to obtain the graphene oxide modified woodware waterborne antibacterial polyurethane coating;
and in the sixth step, the graphene oxide modified woodware waterborne antibacterial polyurethane coating prepared in the fifth step is coated on woodware, then is cured at normal temperature for 5-7 hours, and then is dried in a drying oven.
6. The preparation process of the graphene oxide modified waterborne antibacterial polyurethane coating for woodware according to claim 5, is characterized in that: in the second step, the magnetic stirring time is 15-20 min.
7. The preparation process of the graphene oxide modified waterborne antibacterial polyurethane coating for woodware according to claim 5, is characterized in that: in the third step, the ultrasonic dispersion time is 10-15 min.
8. The preparation process of the graphene oxide modified waterborne antibacterial polyurethane coating for woodware according to claim 5, is characterized in that: in the fourth step, the stirring speed is 600-800r/min, the vacuum drying temperature is 70-90 ℃, and the drying time is 4-7 h.
9. The preparation process of the graphene oxide modified waterborne antibacterial polyurethane coating for woodware according to claim 5, is characterized in that: in the fifth step, the rotation speed of the first emulsification shearing is 700-500 r/min, the emulsification shearing time is 40-60min, the rotation speed of the second emulsification shearing is 300-400r/min, and the emulsification shearing time is 40-60 min.
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