CN113025130B - Anticorrosion, antisludging and antibacterial coating for mold core water well and application thereof - Google Patents
Anticorrosion, antisludging and antibacterial coating for mold core water well and application thereof Download PDFInfo
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- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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Abstract
The invention relates to the technical field of injection molds, and discloses an anticorrosive, scale-inhibiting and antibacterial coating for mold core water wells and application thereof. The coating comprises the following raw materials: fluorocarbon coating with functional groups, curing agent, antibacterial agent and diluent; the mass of the diluent is 0.4-0.6 time of that of the fluorocarbon coating, the mass of the curing agent is 0.1-0.3 time of that of the fluorocarbon coating, and the mass of the antibacterial agent is 0.1-0.3 time of that of the fluorocarbon coating. The coating has good corrosion prevention, scale inhibition and antibacterial effects, and can prevent the problems of water path blockage, cooling efficiency reduction and the like caused by metal corrosion, dirt accumulation, colony formation and the like on the surface of a core water well after being coated on the surface of the core water well of a mold.
Description
Technical Field
The invention relates to the technical field of injection molds, in particular to an anticorrosive, antiscale and antibacterial coating for mold core water wells and application thereof.
Background
In the molding process of the plastic part, the core is always surrounded by the melt with high temperature, therefore, the heat dissipation problem of the core must be improved properly, and the best method for solving the problem is to arrange a water well in the core, and control the temperature of the core by controlling the temperature and flow rate of the cooling water therein, so as to achieve the purpose of heat dissipation of the plastic part. In the core water well, in the process of long-term use, under the combined action of corrosion on the metal surface, dirt accumulation, colony formation and the like, the water channel is often blocked, and the core water well is more easily subjected to dirt accumulation and colony formation due to the slow flow rate of cooling water, while the corrosion of metal enables the former two to be formed more quickly. This not only can cause the cooling efficiency of moulding plastics to descend, and the mould dimension is protected more difficultly, still can cause a series of situations such as water pipe fracture when the scale deposit is especially serious, and this has greatly influenced production efficiency, also is the waste to time, resource simultaneously. At present, the coating which is specially applied to the water channel of the mould is not available in the market, and the coating which has the functions of corrosion prevention, scale inhibition and bacteria resistance is smellless.
Chinese patent publication No. CN107442744A discloses a method for manufacturing a mold having a cooling water passage, comprising: manufacturing a solid core which is consistent with the designed cooling water path and has a smooth outer surface by using a casting process or a 3D printing process; and molding a mold having cooling water paths on the solid core by a casting process. Because the manufactured solid core consistent with the designed cooling water channel has a smooth outer surface, the cooling water channel in the manufactured mould has a smooth inner surface, so that the cooling water channel is not easy to corrode and block, the service life of the mould with the cooling water channel is prolonged, and the production efficiency of the mould is improved. However, although this method of improving the smoothness of the surface of the cooling water channel can improve the corrosion resistance of the water channel, it is difficult to effectively prevent the accumulation of scale and the growth of bacterial colonies.
Disclosure of Invention
In order to solve the technical problems, the invention provides an anticorrosive, scale-inhibiting and antibacterial coating for a mold core water well and application thereof. The coating can effectively prevent the problems of water channel blockage, cooling efficiency reduction and the like caused by metal corrosion, dirt accumulation, colony formation and the like on the surface of a water well of a mold core.
The specific technical scheme of the invention is as follows:
an anticorrosion, antisludging and antibacterial coating for a mold core water well comprises the following raw materials: fluorocarbon coating with functional groups, curing agent, antibacterial agent and diluent; the mass of the diluent is 0.4-0.6 time of that of the fluorocarbon coating, the mass of the curing agent is 0.1-0.3 time of that of the fluorocarbon coating, and the mass of the antibacterial agent is 0.1-0.3 time of that of the fluorocarbon coating.
The coating main body is composed of fluorocarbon coating, a coating can be formed on the surface of a mold core water well by utilizing the matching of functional groups in the fluorocarbon coating and a curing agent, the effects of scale inhibition and corrosion prevention are achieved by the low surface energy and the extremely strong hydrophobic property of a fluorine material, favorable conditions are provided for preventing scale from breeding bacteria, and meanwhile, the antibacterial agent can further improve the antibacterial effect of the coating. Through the way, the coating disclosed by the invention can effectively prevent the problems of water channel blockage, cooling efficiency reduction and the like caused by metal corrosion, dirt accumulation, colony formation and the like on the surface of a water well of a mold core.
Preferably, the fluorocarbon coating with functional groups is one or a combination of any more of epoxy fluorocarbon coating, amino fluorocarbon coating and hydroxyl fluorocarbon coating.
Preferably, the curing agent is one or the combination of any several of nylon 66, epoxy resin E-51, epoxy resin E-44 and polyisocyanate.
Preferably, the diluent is one or a combination of any several of diethylene glycol butyl ether acetate, toluene, ethyl acetate, butyl acetate, methanol and ethanol.
Preferably, the antibacterial agent is chitosan and/or zinc oxide.
Preferably, the fluorocarbon coating with functional groups is a modified hydroxyl fluorocarbon coating, and the preparation method comprises the following steps:
(1) preparation of citric acid-ethylene glycol copolymer: adding citric acid, ethylene glycol and an esterification catalyst into a reaction vessel, and carrying out melt polycondensation reaction to obtain a citric acid-ethylene glycol copolymer;
(2) grafting of palmityl alcohol: adding palm alcohol into a reaction container, and carrying out esterification reaction to obtain a palm alcohol modified copolymer;
(3) modification of fluorocarbon coating: taking 8-10wt% of all hydroxyl fluorocarbon coatings, mixing the hydroxyl fluorocarbon coatings with the modified copolymer according to the mass ratio of 6-8:1, and then carrying out esterification reaction; and cooling the reaction product, and mixing with the rest hydroxy fluorocarbon coating to obtain the modified hydroxy fluorocarbon coating.
In the step (1), through the polycondensation reaction between citric acid and ethylene glycol, a copolymer with high branching degree and a large number of terminal carboxyl groups can be synthesized; in the step (2), the palmityl alcohol and part of terminal carboxyl groups in the citric acid-glycol copolymer are subjected to esterification reaction through hydroxyl groups, so that long paraffin is grafted on the tail end of the copolymer; in the step (3), the hydroxyl fluorocarbon coating and the terminal carboxyl groups in the modified copolymer are subjected to esterification reaction, so that a large number of terminal carboxyl groups are grafted on the hydroxyl fluorocarbon coating.
Under the long-term water flow flushing, the coating on the surface of the core well is easy to damage, so that the corrosion prevention, scale inhibition and antibacterial effects are reduced. Aiming at the problems, the invention adopts the hydroxyl fluorocarbon coating grafted with the citric acid-ethylene glycol copolymer, wherein a large number of terminal carboxyl groups can be complexed with chromium oxide on the surface of the core water well (the surface of the core water well is made of stainless steel materials), thereby increasing the bonding strength between the coating and the core water well, and meanwhile, the interior of the fluorocarbon coating is crosslinked through a curing agent, so that the effect of resisting the water flow scouring of the coating can be improved.
The citric acid-ethylene glycol copolymer is adopted to modify the fluorocarbon coating, so that the coating can be prevented from being damaged under the long-term water flow flushing, and meanwhile, the citric acid-ethylene glycol copolymer has a large number of branched chains and is disordered in structure, so that the heat conductivity is poor, and the cooling efficiency of the core water well is reduced. In order to solve the problems, the invention carries out the palm alcohol graft modification on the citric acid-ethylene glycol copolymer (step (2)), after long paraffin is grafted on the tail end, the ordered arrangement of the paraffin chains is beneficial to the quick and effective heat transfer along the paraffin chains, and the crystallinity of the polymer can be improved, the phonon scattering is reduced, and the heat conductivity of the coating can be improved.
In step (3), only a part of the fluorocarbon coating is reacted with the modified copolymer, and the amount of the part of the fluorocarbon coating is controlled in the range of 8 to 10wt%, because: if the hyperbranched polymer is grafted on the excessive hydroxyl fluorocarbon coating, the carboxyl can cause the hydrophobicity of the coating to be reduced, and the scale inhibition effect is influenced; if too little hydroxyl fluorocarbon coating is grafted with the hyperbranched polymer, the bonding strength between the coating and the sizing sleeve is small, and the improvement effect on long-term scale inhibition is limited.
Preferably, in the step (1), the mass ratio of the ethylene glycol to the citric acid is 1: 5.5-6.5.
Preferably, in step (1), the esterification catalyst is p-toluenesulfonic acid; the mass ratio of the p-toluenesulfonic acid to the ethylene glycol is 1: 10-20.
Preferably, in the step (1), the temperature of the melt polycondensation reaction is 140-150 ℃, the pressure is 0.01-0.05MPa, and the reaction time is 3-4 h.
Preferably, the mass ratio between the palmitic alcohol of step (2) and the citric acid of step (1) is 1:1 to 1.5.
Preferably, in the step (2), the esterification reaction is carried out at the temperature of 120 ℃ and 130 ℃, the pressure is 0.01-0.05MPa, and the reaction time is 0.5-1 h.
Preferably, in the step (3), the temperature of the esterification reaction is 110-120 ℃, and the reaction time is 2-3 h.
The application of the coating in a water well of a mould core comprises the following steps: mixing the fluorocarbon coating with functional groups, a curing agent and a diluent, adding an antibacterial agent, uniformly dispersing to obtain an anticorrosive, scale-inhibiting and antibacterial coating, spraying the anticorrosive, scale-inhibiting and antibacterial coating on the surface of a water well of a mold core, and curing at the temperature of 20-30 ℃ for 1-3h to form an anticorrosive, scale-inhibiting and antibacterial coating.
Compared with the prior art, the invention has the following advantages:
(1) the coating has good anti-corrosion, anti-scaling and anti-bacterial effects, and can prevent the problems of water channel blockage, cooling efficiency reduction and the like on the surface of a water well of a mold core due to metal corrosion, dirt accumulation, colony formation and the like;
(2) the citric acid-ethylene glycol copolymer is adopted to carry out graft modification on the hydroxyl fluorocarbon coating, so that the bonding strength of the coating and the surface of the core water well can be improved, and the coating is prevented from being damaged under the long-term water flushing;
(3) the palm alcohol is grafted at the tail end of the citric acid-ethylene glycol copolymer, so that the heat-conducting property of the coating can be improved, and the influence of the palm alcohol on the cooling efficiency of the core water well is reduced.
Drawings
FIG. 1 is a photograph of the surface of a core well after a machine test; wherein, the pictures (a) - (b) are respectively the pictures of the core water well machine test of the comparative example 1 at 0 month and 1 month, the pictures (c) - (e) are respectively the pictures of the core water well machine test of the example 1 at 0 month, 1 month and 2 months, and the pictures (f) - (h) are respectively the pictures of the core water well machine test of the example 1 at 0 month, 1 month and 2 months;
FIG. 2 shows the growth of bacteria on the surface of a stainless steel plate in an antibacterial test; wherein, FIG. (a) is a stainless steel plate to which the paint was not sprayed, FIG. (b) is a stainless steel plate to which the paint of comparative example 2 was sprayed, and FIG. (c) is a stainless steel plate to which the paint of example 1 was sprayed; green is live bacteria, red is dead bacteria, the figure is a grey scale pattern, the color is not shown.
Detailed Description
The present invention will be further described with reference to the following examples.
General examples
An anticorrosion, antisludging and antibacterial coating for a mold core water well comprises the following raw materials: fluorocarbon coating with functional groups, curing agent, antibacterial agent and diluent; the mass of the diluent is 0.4-0.6 time of that of the fluorocarbon coating, the mass of the curing agent is 0.1-0.3 time of that of the fluorocarbon coating, and the mass of the antibacterial agent is 0.1-0.3 time of that of the fluorocarbon coating.
The fluorocarbon coating with functional groups is one or the combination of any more of epoxy fluorocarbon coating, amino fluorocarbon coating and hydroxyl fluorocarbon coating. The curing agent is one or the combination of any more of nylon 66, epoxy resin E-51, epoxy resin E-44 and polyisocyanate. The diluent is one or the combination of any more of diethylene glycol butyl ether acetate, toluene, ethyl acetate, butyl acetate, methanol and ethanol. The antibacterial agent is chitosan and/or zinc oxide.
Optionally, the fluorocarbon coating with functional groups is a modified hydroxy fluorocarbon coating, and the preparation method thereof is as follows:
(1) preparation of citric acid-ethylene glycol copolymer: adding citric acid, ethylene glycol and an esterification catalyst in a mass ratio of 5.5-6.5:1:0.05-0.1 into a reaction vessel, and carrying out melt polycondensation reaction at the temperature of 140-;
(2) grafting of palmityl alcohol: adding the palm alcohol into a reaction container, wherein the mass ratio of the palm alcohol to the citric acid in the step (1) is 1:1-1.5, and carrying out esterification reaction at the temperature of 120-;
(3) modification of fluorocarbon coating: 8-10wt% of all hydroxyl fluorocarbon coatings are mixed with the modified copolymer according to the mass ratio of 6-8:1, and then esterification reaction is carried out at the temperature of 110-120 ℃, and the reaction time is 2-3 h; and cooling the reaction product, and mixing with the rest hydroxy fluorocarbon coating to obtain the modified hydroxy fluorocarbon coating.
The coating is applied to a mold core water well, and the specific method comprises the following steps: mixing the fluorocarbon coating with functional groups, a curing agent and a diluent, adding an antibacterial agent, uniformly dispersing to obtain an anticorrosive, scale-inhibiting and antibacterial coating, spraying the anticorrosive, scale-inhibiting and antibacterial coating on the surface of a water well of a mold core, and curing at the temperature of 20-30 ℃ for 1-3h to form an anticorrosive, scale-inhibiting and antibacterial coating.
Example 1
An anticorrosion, antisludging and antibacterial coating for a mold core water well comprises the following raw materials: hydroxyl fluorocarbon paint, polyisocyanate, zinc oxide, diethylene glycol butyl ether acetate; the mass of the diethylene glycol monobutyl ether acetate is 0.5 time of that of the hydroxyl fluorocarbon coating, the mass of the polyisocyanate is 0.2 time of that of the hydroxyl fluorocarbon coating, and the mass of the zinc oxide is 0.1 time of that of the hydroxyl fluorocarbon coating.
The coating is applied to a mold core water well, and the specific method comprises the following steps: mixing the hydroxyl fluorocarbon coating, polyisocyanate and diethylene glycol butyl ether acetate, adding zinc oxide, dispersing uniformly to obtain the anticorrosive, scale-inhibiting and antibacterial coating, spraying the anticorrosive, scale-inhibiting and antibacterial coating on the surface of a water well of a mold core, and curing for 3 hours at normal temperature to form an anticorrosive, scale-inhibiting and antibacterial coating with the average thickness of 10 mu m.
Example 2
An anticorrosion, antisludging and antibacterial coating for a mold core water well comprises the following raw materials: modified hydroxyl fluorocarbon coating, polyisocyanate, zinc oxide and diethylene glycol butyl ether acetate; the mass of the diethylene glycol monobutyl ether acetate is 0.5 time of that of the modified hydroxyl fluorocarbon coating, the mass of the polyisocyanate is 0.2 time of that of the modified hydroxyl fluorocarbon coating, and the mass of the zinc oxide is 0.1 time of that of the modified hydroxyl fluorocarbon coating.
The preparation method of the modified hydroxyl fluorocarbon coating comprises the following steps:
(1) preparation of citric acid-ethylene glycol copolymer: adding citric acid, ethylene glycol and p-toluenesulfonic acid in a mass ratio of 6:1:0.08 into a reaction kettle, and carrying out melt polycondensation reaction at 145 ℃ and 0.03MPa for 3-4h to obtain a citric acid-ethylene glycol copolymer;
(2) grafting of palmityl alcohol: adding palm alcohol into a reaction kettle, wherein the mass ratio of the palm alcohol to the citric acid in the step (1) is 1:1.2, and carrying out esterification reaction at 125 ℃ and under 0.03MPa for 0.5-1h to obtain a palm alcohol modified copolymer;
(3) modification of fluorocarbon coating: taking 9 wt% of all hydroxyl fluorocarbon coatings, mixing the hydroxyl fluorocarbon coatings with the modified copolymer according to the mass ratio of 7:1, and then carrying out esterification reaction at 115 ℃ for 2.5 hours; and cooling the reaction product, and mixing with the rest hydroxy fluorocarbon coating to obtain the modified hydroxy fluorocarbon coating.
The coating is applied to a mold core water well, and the specific method comprises the following steps: mixing the modified hydroxyl fluorocarbon coating, polyisocyanate and diethylene glycol butyl ether acetate, adding zinc oxide, dispersing uniformly to obtain the anticorrosive, scale-inhibiting and antibacterial coating, spraying the anticorrosive, scale-inhibiting and antibacterial coating on the surface of a water well of a mold core, and curing for 3 hours at normal temperature to form an anticorrosive, scale-inhibiting and antibacterial coating with the average thickness of 10 mu m.
Comparative example 1
The comparative example does not spray anticorrosive, scale-inhibiting and antibacterial coatings on the surface of the water well of the mold core.
Comparative example 2
The coating for the water well of the mold core comprises the following raw materials: hydroxyl fluorocarbon paint, polyisocyanate, diethylene glycol butyl ether acetate; the mass of the diethylene glycol monobutyl ether acetate is 0.5 time of that of the hydroxyl fluorocarbon coating, and the mass of the polyisocyanate is 0.2 time of that of the hydroxyl fluorocarbon coating.
The coating is applied to a mold core water well, and the specific method comprises the following steps: the hydroxyl fluorocarbon coating, polyisocyanate and diethylene glycol butyl ether acetate are uniformly mixed to obtain the coating, the coating is sprayed on the surface of a water well of a mold core and cured for 3 hours at normal temperature to form an anticorrosive, scale-inhibiting and antibacterial coating with the average thickness of 10 mu m.
Comparative example 3
An anticorrosion, antisludging and antibacterial coating for a mold core water well comprises the following raw materials: modified hydroxyl fluorocarbon coating, polyisocyanate, zinc oxide and diethylene glycol butyl ether acetate; the mass of the diethylene glycol monobutyl ether acetate is 0.5 time of that of the modified hydroxyl fluorocarbon coating, the mass of the polyisocyanate is 0.2 time of that of the modified hydroxyl fluorocarbon coating, and the mass of the zinc oxide is 0.1 time of that of the modified hydroxyl fluorocarbon coating.
The preparation method of the modified hydroxyl fluorocarbon coating comprises the following steps:
(1) preparation of citric acid-ethylene glycol copolymer: adding citric acid, ethylene glycol and p-toluenesulfonic acid in a mass ratio of 6:1:0.08 into a reaction kettle, and carrying out melt polycondensation reaction at 145 ℃ and 0.03MPa for 3-4h to obtain a citric acid-ethylene glycol copolymer;
(2) modification of fluorocarbon coating: taking 9 wt% of all hydroxyl fluorocarbon coatings, mixing the hydroxyl fluorocarbon coatings with citric acid-ethylene glycol copolymer according to the mass ratio of 7:1, and then carrying out esterification reaction at 115 ℃ for 2.5 hours; and cooling the reaction product, and mixing with the rest hydroxy fluorocarbon coating to obtain the modified hydroxy fluorocarbon coating.
The coating is applied to a mold core water well, and the specific method comprises the following steps: mixing the modified hydroxyl fluorocarbon coating, polyisocyanate and diethylene glycol butyl ether acetate, adding zinc oxide, dispersing uniformly to obtain the anticorrosive, scale-inhibiting and antibacterial coating, spraying the anticorrosive, scale-inhibiting and antibacterial coating on the surface of a water well of a mold core, and curing for 3 hours at normal temperature to form an anticorrosive, scale-inhibiting and antibacterial coating with the average thickness of 10 mu m.
Comparative example 4
An anticorrosion, antisludging and antibacterial coating for a mold core water well comprises the following raw materials: modified hydroxyl fluorocarbon coating, polyisocyanate, zinc oxide and diethylene glycol butyl ether acetate; the mass of the diethylene glycol monobutyl ether acetate is 0.5 time of that of the modified hydroxyl fluorocarbon coating, the mass of the polyisocyanate is 0.2 time of that of the modified hydroxyl fluorocarbon coating, and the mass of the zinc oxide is 0.1 time of that of the modified hydroxyl fluorocarbon coating.
The preparation method of the modified hydroxyl fluorocarbon coating comprises the following steps:
(1) preparation of citric acid-ethylene glycol copolymer: adding citric acid, ethylene glycol and p-toluenesulfonic acid in a mass ratio of 6:1:0.08 into a reaction kettle, and carrying out melt polycondensation reaction at 145 ℃ and 0.03MPa for 3-4h to obtain a citric acid-ethylene glycol copolymer;
(2) grafting of palmityl alcohol: adding palm alcohol into a reaction kettle, wherein the mass ratio of the palm alcohol to the citric acid in the step (1) is 1:1.2, and carrying out esterification reaction at 125 ℃ and under 0.03MPa for 0.5-1h to obtain a palm alcohol modified copolymer;
(3) modification of fluorocarbon coating: taking 6 wt% of all hydroxyl fluorocarbon coatings, mixing the hydroxyl fluorocarbon coatings with the modified copolymer according to the mass ratio of 7:1, and then carrying out esterification reaction at 115 ℃ for 2.5 hours; and cooling the reaction product, and mixing with the rest hydroxy fluorocarbon coating to obtain the modified hydroxy fluorocarbon coating.
The coating is applied to a mold core water well, and the specific method comprises the following steps: mixing the modified hydroxyl fluorocarbon coating, polyisocyanate and diethylene glycol butyl ether acetate, adding zinc oxide, dispersing uniformly to obtain the anticorrosive, scale-inhibiting and antibacterial coating, spraying the anticorrosive, scale-inhibiting and antibacterial coating on the surface of a water well of a mold core, and curing for 3 hours at normal temperature to form an anticorrosive, scale-inhibiting and antibacterial coating with the average thickness of 10 mu m.
Comparative example 5
An anticorrosion, antisludging and antibacterial coating for a mold core water well comprises the following raw materials: modified hydroxyl fluorocarbon coating, polyisocyanate, zinc oxide and diethylene glycol butyl ether acetate; the mass of the diethylene glycol monobutyl ether acetate is 0.5 time of that of the modified hydroxyl fluorocarbon coating, the mass of the polyisocyanate is 0.2 time of that of the modified hydroxyl fluorocarbon coating, and the mass of the zinc oxide is 0.1 time of that of the modified hydroxyl fluorocarbon coating.
The preparation method of the modified hydroxyl fluorocarbon coating comprises the following steps:
(1) preparation of citric acid-ethylene glycol copolymer: adding citric acid, ethylene glycol and p-toluenesulfonic acid in a mass ratio of 6:1:0.08 into a reaction kettle, and carrying out melt polycondensation reaction at 145 ℃ and 0.03MPa for 3-4h to obtain a citric acid-ethylene glycol copolymer;
(2) grafting of palmityl alcohol: adding palm alcohol into a reaction kettle, wherein the mass ratio of the palm alcohol to the citric acid in the step (1) is 1:1.2, and carrying out esterification reaction at 125 ℃ and under 0.03MPa for 0.5-1h to obtain a palm alcohol modified copolymer;
(3) modification of fluorocarbon coating: taking 12 wt% of all hydroxyl fluorocarbon coatings, mixing the hydroxyl fluorocarbon coatings with the modified copolymer according to the mass ratio of 7:1, and then carrying out esterification reaction at 115 ℃ for 2.5 hours; and cooling the reaction product, and mixing with the rest hydroxy fluorocarbon coating to obtain the modified hydroxy fluorocarbon coating.
The coating is applied to a mold core water well, and the specific method comprises the following steps: mixing the modified hydroxyl fluorocarbon coating, polyisocyanate and diethylene glycol butyl ether acetate, adding zinc oxide, dispersing uniformly to obtain the anticorrosive, scale-inhibiting and antibacterial coating, spraying the anticorrosive, scale-inhibiting and antibacterial coating on the surface of a water well of a mold core, and curing for 3 hours at normal temperature to form an anticorrosive, scale-inhibiting and antibacterial coating with the average thickness of 10 mu m.
Test example
1 coating antibacterial Properties
The coatings prepared in example 1 and comparative example 2 were sprayed on the surface of a stainless steel plate, after culturing at 37 ℃ for 24 hours, viable bacteria and dead bacteria were distinguished by dyeing, so that the viable bacteria appeared in green and the dead bacteria appeared in red, and the growth of the bacteria on the surface of the stainless steel plate with and without the coatings was observed, and the results are shown in fig. 2.
As can be seen from fig. 2: after the culture, a large number of viable bacteria appeared on the surface of the stainless steel plate (FIG. 2(a)) on which the coating was not sprayed, whereas the number of cells on the surface of the stainless steel plate (FIG. 2(b)) on which the coating of comparative example 2 was sprayed was significantly reduced as compared with that of FIG. 2(a), whereas the number of cells on the surface of the stainless steel plate (FIG. 2(b)) on which the coating of example 1 was sprayed was similar to that of FIG. 2(b), but some of the viable bacteria were changed into dead bacteria.
2 machine test
After the core wells of examples 1 to 2 and comparative example 1 were loaded on the mold, the on-machine test was performed, and the surface of the core well was observed for scale accumulation and colony growth at 0 month, 1 month, and 2 months, respectively, and the results are shown in fig. 1.
As can be seen from fig. 1: when the core water well is tested on the machine for 1 month, a large amount of rust, scale and bacterial colonies appear on the surface of the core water well which is not sprayed with the coating, and the core water well cannot be used any more, and the surface of the core water well which is sprayed with the coatings of the examples 1 and 2 is basically kept clean; after 2 months, the surface of the core well of example 1 showed a small amount of scale and rust, while the surface of the core well of example 2 remained clean.
After the core wells of examples 1-2 and comparative examples 1-5 were loaded on the mold, the on-machine test was performed, and 5 spots were taken on the surface of each core well at 0 month, 1 month, 2 months, and 3 months, respectively, and the results were shown in table 1 after detecting the contact angle.
TABLE 1
| 0 month | 1 month | 2 months old | 3 months old | |
| Example 1 | 138.85 | 132.50 | 123.54 | 112.95 |
| Example 2 | 133.05 | 130.67 | 128.01 | 125.36 |
| Comparative example 1 | 62.34 | 0 | 0 | 0 |
| Comparative example 2 | 117.33 | 114.28 | 108.94 | 101.62 |
| Comparative example 3 | 134.80 | 131.02 | 126.80 | 119.43 |
| Comparative example 4 | 135.69 | 131.47 | 125.86 | 118.95 |
| Comparative example 5 | 128.36 | 126.58 | 123.95 | 120.03 |
As can be seen from table 1:
(1) at 0 months, the contact angle of the water well surface of the core is more than that of the embodiment 1 and the comparative example 2 and the comparative example 1. The above results show that: by spraying fluorocarbon coating, the hydrophobicity and antifouling and scale inhibiting capability of the surface of the core water well can be improved; after the zinc oxide antibacterial agent is added into the fluorocarbon coating, the hydrophobicity of the surface of the core water well is further improved. The reason is presumed to be: the surface of the coating taking the fluorocarbon coating as the main body has lower energy and extremely strong hydrophobicity, thereby playing the roles of inhibiting scale and corrosion and preventing bacteria from breeding; after the zinc oxide is added into the fluorocarbon coating, a micro-coarse structure can be formed on the surface of the coating, and the hydrophobicity of the coating is further improved.
(2) At month 3, the contact angles of the water well surfaces of the inserts of example 2 and comparative example 3 were larger compared to example 1. The above results show that: the citric acid-ethylene glycol copolymer is adopted to modify the fluorocarbon coating, so that the long-term scale inhibition effect of the coating can be improved. The reason is presumed to be: the citric acid-ethylene glycol copolymer contains a large amount of carboxyl end groups, and can be complexed with chromium oxide on the surface of the core well (the surface of the core well is made of stainless steel), so that the bonding strength between the coating and the core well is increased, and meanwhile, the interior of the fluorocarbon coating is crosslinked through a curing agent, so that the effect of resisting the water flow scouring of the coating can be improved.
(3) At month 3, the contact angle of the surface of the cored water well of comparative example 4 was smaller compared to example 2; at 0 months, the insert of comparative example 5 had a lower water well contact angle than example 2. The above results show that: when the amount of the hydroxy fluorocarbon coating modified by the citric acid-ethylene glycol copolymer is too small, the long-term scale inhibition effect of the coating is poor; when too much hydroxy fluorocarbon coating modified by citric acid-ethylene glycol copolymer is adopted, the scale inhibition effect of the coating is poor. The reason is presumed to be: if the hyperbranched polymer is grafted on the excessive hydroxyl fluorocarbon coating, the carboxyl can cause the hydrophobicity of the coating to be reduced, and the scale inhibition effect is influenced; if too little hydroxyl fluorocarbon coating is grafted with the hyperbranched polymer, the bonding strength between the coating and the sizing sleeve is small, and the improvement effect on long-term scale inhibition is limited.
3 heat-conducting property of coating
The coatings obtained in examples 1-2 and comparative example 3 were subjected to a thermal conductivity test, and the results are shown in Table 2.
TABLE 2
| Thermal conductivity (W/(m.K)) | |
| Example 1 | 1.28 |
| Example 2 | 0.57 |
| Comparative example 3 | 1.02 |
As can be seen from table 2: after the citric acid-ethylene glycol copolymer is adopted to graft modify the hydroxyl fluorocarbon coating, the heat conductivity coefficient of the coating is obviously reduced; however, when the citric acid-ethylene glycol copolymer modified by the palmityl alcohol is adopted, the reduction range of the thermal conductivity of the coating is small. The reason is presumed to be: the citric acid-ethylene glycol copolymer has a large number of branched chains and disordered structure, so that the thermal conductivity is poor; the citric acid-ethylene glycol copolymer is subjected to palm alcohol grafting modification, after long paraffin is grafted at the tail end, the paraffin chains are orderly arranged, so that heat can be rapidly and effectively transferred along the paraffin chains, the crystallinity of the polymer can be improved, phonon scattering is reduced, and the heat conductivity of the coating can be improved.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (5)
1. The anti-corrosion, anti-scaling and antibacterial coating for the mold core water well is characterized by comprising the following raw materials: fluorocarbon coating with functional groups, curing agent, antibacterial agent and diluent; the mass of the diluent is 0.4-0.6 time of that of the fluorocarbon coating, the mass of the curing agent is 0.1-0.3 time of that of the fluorocarbon coating, and the mass of the antibacterial agent is 0.1-0.3 time of that of the fluorocarbon coating; the fluorocarbon coating with functional groups is a modified hydroxyl fluorocarbon coating, and the preparation method comprises the following steps:
(1) preparation of citric acid-ethylene glycol copolymer: adding citric acid, ethylene glycol and an esterification catalyst into a reaction vessel, wherein the mass ratio of the ethylene glycol to the citric acid is 1:5.5-6.5, and carrying out melt polycondensation reaction at the temperature of 140-;
(2) grafting of palmityl alcohol: adding the palm alcohol into a reaction container, wherein the mass ratio of the palm alcohol in the step (2) to the citric acid in the step (1) is 1:1-1.5, and carrying out esterification reaction at the temperature of 120-130 ℃ and under the pressure of 0.01-0.05MPa for 0.5-1h to obtain a palm alcohol modified copolymer;
(3) modification of fluorocarbon coating: 8-10wt% of all hydroxyl fluorocarbon coatings are mixed with the modified copolymer according to the mass ratio of 6-8:1, and then esterification reaction is carried out for 2-3h at the temperature of 110-; and cooling the reaction product, and mixing with the rest hydroxy fluorocarbon coating to obtain the modified hydroxy fluorocarbon coating.
2. The coating of claim 1, wherein the curing agent is one or a combination of any of epoxy resin E-51, epoxy resin E-44, and polyisocyanate.
3. The paint as claimed in claim 1 or 2, wherein the diluent is one or a combination of any of diethylene glycol butyl ether acetate, toluene, ethyl acetate, butyl acetate, methanol and ethanol.
4. The coating of claim 1, wherein the antimicrobial agent is chitosan and/or zinc oxide.
5. Use of a coating according to any of claims 1 to 4 in a water well of a mould core, comprising the steps of: mixing the fluorocarbon coating with functional groups, a curing agent and a diluent, adding an antibacterial agent, uniformly dispersing to obtain an anticorrosive, scale-inhibiting and antibacterial coating, spraying the anticorrosive, scale-inhibiting and antibacterial coating on the surface of a water well of a mold core, and curing at the temperature of 20-30 ℃ for 1-3h to form an anticorrosive, scale-inhibiting and antibacterial coating.
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