CN113337176A - Non-stick pan coating based on interpenetrating network structure and preparation method thereof - Google Patents
Non-stick pan coating based on interpenetrating network structure and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of non-stick pan coatings, in particular to a non-stick pan coating based on an interpenetrating network structure, which is formed by mixing an epoxy resin system and a polyurethane resin system according to a mass ratio of 5-7: 2-3; the epoxy resin system comprises the following components in parts by mass: 30-50 parts of alicyclic epoxy compound, 80-90 parts of glycidyl amine type resin, 3-5 parts of modified carbon fiber, 2-5 parts of pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hydroxyhydrocinnamate), 3-5 parts of zirconia ceramic, 11-12 parts of alumina ceramic, 10-15 parts of zinc oxide ceramic, 13-17 parts of silicon nitride ceramic and 2-5 parts of polyethylene wax. The invention has a uniform resin crosslinking system, can be tightly connected with filled zirconia ceramics, alumina ceramics, zinc oxide ceramics and silicon nitride ceramics, so that the prepared coating not only can keep the high-temperature resistant effect of epoxy resin, but also can keep the elasticity of polyurethane, has good stability at high temperature, can adapt to the high-temperature swelling effect of a pot body, and improves the integrity of a non-stick pot.
Description
Technical Field
The invention relates to the technical field of non-stick pan coatings, in particular to a non-stick pan coating based on an interpenetrating network structure and a preparation method thereof.
Background
The frying pan is a traditional kitchen ware, still has not few families to use the frying pan to cook food to the present, and the frying pan cooks food and has more shortcoming, and general frying pan is made by ferroalloy, and its heat distributes unevenly, easily produces and gathers hot spot and burn food, and its pot weight is difficult to wash, easily rusts, and the oil smoke is big when using much oil. So that the wok is usually made into a non-stick wok by adding the coating in the wok.
The interpenetrating network polymer is formed by intersecting and interpenetrating multi-molecular chain substances, so that the formed coating has various effects, and the defect of food burning in the conventional frying pan can be effectively avoided.
However, the non-stick pan using the coating in the prior art is easy to scratch and rub and cannot resist high-strength cleaning. For example, a non-stick coating, its preparation method and pot tool of patent No. CN202010766162.1, wherein a middle layer film is formed on a substrate by a middle layer paint, and an outer layer film is formed on one side of the middle layer film, which faces away from the substrate, by an outer layer paint; heating and curing the middle layer film and the outer layer film, forming a middle coating after curing the middle layer film, and forming an outer coating after curing the outer layer film, but the middle coating has a single adhesive body and poor durability of the middle coating in cooking at high temperature; for another example, a preparation method of a high-temperature-resistant wear-resistant non-stick pan coating with patent number CN202010690462.6 is formed by spraying MOFs, fluororesin emulsion, fluorine-containing silane coupling agent and the like, but the coating is difficult to adapt to expansion and contraction of a pan body in frequent temperature change of a frying pan due to overhigh mechanical strength, so that the coating is easy to peel off after long-term use. Therefore, it is necessary to research a coating layer integrating various adhesive properties to improve the performance of the non-stick pan by using interpenetrating network polymer as a core.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a non-stick pan coating based on an interpenetrating network structure and a preparation method thereof, so as to strengthen the bonding between the coating and a pan body and improve the durability of the non-stick pan. The specific technical scheme is as follows:
a non-stick pan coating based on an interpenetrating network structure is formed by mixing an epoxy resin system and a polyurethane resin system according to a mass ratio of 5-7: 2-3; the epoxy resin system comprises the following components in parts by mass: 30-50 parts of alicyclic epoxy compound, 80-90 parts of glycidyl amine type resin, 3-5 parts of modified carbon fiber, 2-5 parts of pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hydroxyhydrocinnamate), 3-5 parts of zirconia ceramic, 11-12 parts of alumina ceramic, 10-15 parts of zinc oxide ceramic, 13-17 parts of silicon nitride ceramic and 2-5 parts of polyethylene wax;
the polyurethane resin system includes: 35-40 parts of isocyanate-terminated polyurethane prepolymer, 3-5 parts of modified graphene, 5-8 parts of polyamide resin and 10-18 parts of triethylene tetramine; .
Further, the preparation method of the modified carbon fiber comprises the following steps: mixing pyromellitic dianhydride and ethylenediamine according to a molar mass ratio of 2:3-5, pouring into a reaction container, adding quinoline and acetone, uniformly mixing, reacting for 15-19h at 70-80 ℃ in a water bath, putting the pretreated carbon fiber into the solution, and performing ultrasonic treatment for 7-12 min; and centrifuging, washing the carbon fiber with ethanol, and drying to obtain the modified carbon fiber.
Further, the preparation method of the modified graphene comprises the following steps: mixing the carboxylated graphene and acetone according to the mass ratio of 1:5-8, adding diethyltoluenediamine, mixing, raising the temperature to 140-.
Furthermore, the zirconia ceramic, the alumina ceramic, the zinc oxide ceramic and the silicon nitride ceramic are powder with the uniform fineness of 80-150 nm.
Furthermore, the using amount of the quinoline is 1-3% of the mass of the pyromellitic dianhydride.
Furthermore, the amount of the acetone is 8-10 times of the mass of the pyromellitic dianhydride.
Further, the pretreatment of the carbon fiber is as follows: heating the carbon fiber to 800-.
Further, the using amount of the carbon fiber is 45-65% of the mass of the pyromellitic dianhydride.
Furthermore, the dosage of the diethyl toluene diamine is 4-6 times of the mass of the carboxylated graphene.
The invention relates to a preparation method of a non-stick pan coating based on an interpenetrating network structure, which comprises the following steps:
(1) preparation of the epoxy resin system:
uniformly mixing an alicyclic epoxy compound, a glycidyl amine type resin, polyethylene wax and pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hydroxyhydrocinnamate) according to the mass ratio, sequentially adding modified carbon fibers, zirconia ceramics, alumina ceramics, zinc oxide ceramics and silicon nitride ceramics, and uniformly stirring for later use;
(2) preparation of polyurethane resin system:
uniformly mixing the isocyanate-terminated polyurethane prepolymer, the modified graphene, the polyamide resin and the triethylene tetramine, and homogenizing under high pressure for later use;
(3) mixing and spraying the epoxy resin system and the polyurethane resin system according to the mass ratio, and heating to 150-170 ℃ for curing.
The preparation method of the isocyanate-terminated polyurethane prepolymer comprises the following steps: under the protection of nitrogen, 1 part of dehydrated polyethylene glycol 2000 and 3 parts of isophorone diisocyanate are added into a four-neck flask, 0.1 part of dibutyltin dilaurate is added, and the mixture is heated to 70 ℃ under the dissolution of 10 parts of acetone to obtain the product after the reaction is finished.
The invention has the beneficial effects that:
the invention utilizes polar groups such as ether groups, ester groups and the like which are rich in polyurethane molecular chains, hydrogen bonds with sufficient quantity exist in the interior and among molecules of the polyurethane molecular chains, hydroxyl groups and epoxy groups in the epoxy resin have high activity, the compatibility of the hydroxyl groups and the epoxy groups is good, and the epoxy resin is easy to crosslink, so that a uniform resin crosslinking system is formed and can be tightly connected with filled zirconia ceramics, alumina ceramics, zinc oxide ceramics and silicon nitride ceramics. The prepared coating can keep the high-temperature resistant effect of the epoxy resin and the elasticity of the polyurethane, has good stability at high temperature, can adapt to the swelling effect of the high temperature of the pot body, and improves the integrity of the non-stick pot.
According to the invention, the carbon fiber is treated at high temperature, so that the hybrid groups in the carbon fiber are removed, and the number of carbon-oxygen active groups on the surface of the carbon fiber is increased in an aromatic condensed ring amide solution by utilizing the pi-pi action among aromatic condensed rings. The fusion of the carbon fiber and the resin system is enhanced, and the high-temperature stability and the durability of the coating are improved.
According to the invention, the surface of graphene is connected by using diethyl toluene diamine, and the steric hindrance effect brought by multiple branches of diethyl toluene diamine is utilized, so that multiple amino groups in the same molecule are simultaneously connected by carboxyl, the connection effect of a single amino group is improved, more amino groups are on the surface of graphene, and the solidification of an epoxy resin system can be remarkably promoted. And a large number of polymer groups are brought in a resin system, so that the rigidity of the coating under a high-temperature effect is obviously improved, the shrinkage and expansion of the whole coating under a large temperature difference tend to be microscopic, and the fitting degree of the coating and the pot body is improved.
According to the method, the graphene oxide surface has certain defects, and the resin molecular network longitudinally passes through the two-dimensional graphene network through the defects by mixing the two resin systems, and is connected with the amino on the graphene surface and the chemical bond of the resin system to form an organic whole, so that the beam-closing capacity of the graphene network on the resin system is improved. And the interface bonding degree of the activated carbon fiber and the resin bonding system is increased, a three-dimensional radial bonding network is formed around the graphene, the complete coating is formed on the outer part of the graphene, the longitudinal and transverse bonding strength of the resin system is further enhanced, the uniformity, compactness and molecular bonding strength of the coating are obviously improved, the coating keeps good cohesiveness and stability in various use environments, and the abrasion caused by frequent high and low temperature changes is reduced.
Detailed Description
Example 1
A non-stick pan coating based on an interpenetrating network structure is formed by mixing an epoxy resin system and a polyurethane resin system according to a mass ratio of 5: 2; the epoxy resin system comprises the following components in parts by mass: 30 parts of alicyclic epoxy compound, 80 parts of glycidyl amine type resin, 3 parts of modified carbon fiber, 2 parts of tetra (3, 5-di-tert-butyl-4-hydroxyhydrocinnamic acid) pentaerythritol ester, 3 parts of zirconia ceramic, 11 parts of alumina ceramic, 10 parts of zinc oxide ceramic, 13 parts of silicon nitride ceramic and 2 parts of polyethylene wax;
the preparation method of the modified carbon fiber comprises the following steps: mixing pyromellitic dianhydride and ethylenediamine according to a molar mass ratio of 2:3, pouring into a reaction container, adding quinoline and acetone, uniformly mixing, reacting for 15h at 70 ℃ in a water bath, putting the pretreated carbon fiber into the solution, and performing ultrasonic treatment for 7 min; centrifuging, washing the carbon fiber with ethanol, and drying to obtain the modified carbon fiber; the amount of the quinoline is 1 percent of the mass of the pyromellitic dianhydride; the amount of the acetone is 8 times of the mass of the pyromellitic dianhydride; the pretreatment of the carbon fiber comprises the following steps: heating the carbon fiber to 800 ℃ in a vacuum environment, and firing for 2 h; the using amount of the carbon fiber is 45 percent of the mass of the pyromellitic dianhydride; the zirconia ceramic, the alumina ceramic, the zinc oxide ceramic and the silicon nitride ceramic are powder with uniform fineness of 80 nm;
the polyurethane resin system includes: 35 parts of isocyanate-terminated polyurethane prepolymer, 3 parts of modified graphene, 5 parts of polyamide resin and 10 parts of triethylene tetramine; the preparation method of the modified graphene comprises the following steps: mixing carboxylated graphene and acetone according to the mass ratio of 1:5, adding diethyl toluene diamine, mixing, raising the temperature to 140 ℃, reacting for 1h, drying under reduced pressure, and washing residues with ethanol for 1 time to obtain modified graphene; the dosage of the diethyl toluene diamine is 4 times of the mass of the carboxylated graphene.
The preparation method of the non-stick pan coating based on the interpenetrating network structure comprises the following steps:
(1) preparation of the epoxy resin system:
uniformly mixing an alicyclic epoxy compound, a glycidyl amine type resin, polyethylene wax and pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hydroxyhydrocinnamate) according to the mass ratio, sequentially adding modified carbon fibers, zirconia ceramics, alumina ceramics, zinc oxide ceramics and silicon nitride ceramics, and uniformly stirring for later use;
(2) preparation of polyurethane resin system:
uniformly mixing the isocyanate-terminated polyurethane prepolymer, the modified graphene, the polyamide resin and the triethylene tetramine, and homogenizing under high pressure for later use;
(3) mixing and spraying an epoxy resin system and a polyurethane resin system according to a mass ratio, and heating to 150 ℃ for curing.
Example 2
A non-stick pan coating based on an interpenetrating network structure is formed by mixing an epoxy resin system and a polyurethane resin system according to a mass ratio of 7: 3; the epoxy resin system comprises the following components in parts by mass: 50 parts of alicyclic epoxy compound, 90 parts of glycidyl amine type resin, 5 parts of modified carbon fiber, 5 parts of tetra (3, 5-di-tert-butyl-4-hydroxyhydrocinnamic acid) pentaerythritol ester, 5 parts of zirconia ceramic, 12 parts of alumina ceramic, 15 parts of zinc oxide ceramic, 17 parts of silicon nitride ceramic and 5 parts of polyethylene wax; the preparation method of the modified carbon fiber comprises the following steps: mixing pyromellitic dianhydride and ethylenediamine according to a molar mass ratio of 2:5, pouring into a reaction container, adding quinoline and acetone, uniformly mixing, reacting for 19h in a water bath at 80 ℃, putting the pretreated carbon fiber into the solution, and performing ultrasonic treatment for 12 min; centrifuging, washing the carbon fiber with ethanol, and drying to obtain the modified carbon fiber; the amount of the quinoline is 3 percent of the mass of the pyromellitic dianhydride; the amount of the acetone is 10 times of the mass of the pyromellitic dianhydride; the pretreatment of the carbon fiber comprises the following steps: heating the carbon fiber to 1000 ℃ in a vacuum environment, and firing for 4 h; the using amount of the carbon fiber is 65 percent of the mass of the pyromellitic dianhydride; the zirconia ceramic, the alumina ceramic, the zinc oxide ceramic and the silicon nitride ceramic are powder with uniform fineness of 150 nm;
the polyurethane resin system includes: 40 parts of isocyanate-terminated polyurethane prepolymer, 5 parts of modified graphene, 8 parts of polyamide resin and 18 parts of triethylene tetramine; the preparation method of the modified graphene comprises the following steps: mixing carboxylated graphene and acetone according to the mass ratio of 1:8, adding diethyl toluene diamine, mixing, raising the temperature to 150 ℃, reacting for 2 hours, drying under reduced pressure, and washing residues with ethanol for 2 times to obtain modified graphene; the dosage of the diethyl toluene diamine is 6 times of the mass of the carboxylated graphene.
The preparation method of the non-stick pan coating based on the interpenetrating network structure comprises the following steps:
(1) preparation of the epoxy resin system:
uniformly mixing an alicyclic epoxy compound, a glycidyl amine type resin, polyethylene wax and pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hydroxyhydrocinnamate) according to the mass ratio, sequentially adding modified carbon fibers, zirconia ceramics, alumina ceramics, zinc oxide ceramics and silicon nitride ceramics, and uniformly stirring for later use;
(2) preparation of polyurethane resin system:
uniformly mixing the isocyanate-terminated polyurethane prepolymer, the modified graphene, the polyamide resin and the triethylene tetramine, and homogenizing under high pressure for later use;
(3) mixing and spraying an epoxy resin system and a polyurethane resin system according to a mass ratio, and heating to 170 ℃ for curing.
Example 3
A non-stick pan coating based on an interpenetrating network structure is formed by mixing an epoxy resin system and a polyurethane resin system according to a mass ratio of 6: 2.7; the epoxy resin system comprises the following components in parts by mass: 40 parts of alicyclic epoxy compound, 86 parts of glycidyl amine type resin, 4 parts of modified carbon fiber, 5 parts of pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hydroxyhydrocinnamate), 5 parts of zirconia ceramic, 11 parts of alumina ceramic, 10 parts of zinc oxide ceramic, 17 parts of silicon nitride ceramic and 5 parts of polyethylene wax;
the preparation method of the modified carbon fiber comprises the following steps: mixing pyromellitic dianhydride and ethylenediamine according to a molar mass ratio of 2:5, pouring into a reaction container, adding quinoline and acetone, uniformly mixing, reacting for 19h in a water bath at 80 ℃, putting the pretreated carbon fiber into the solution, and performing ultrasonic treatment for 12 min; centrifuging, washing the carbon fiber with ethanol, and drying to obtain the modified carbon fiber; the amount of the quinoline is 3 percent of the mass of the pyromellitic dianhydride; the amount of the acetone is 8 times of the mass of the pyromellitic dianhydride; the pretreatment of the carbon fiber comprises the following steps: heating the carbon fiber to 1000 ℃ in a vacuum environment, and firing for 2 h; the using amount of the carbon fiber is 65 percent of the mass of the pyromellitic dianhydride; the zirconia ceramic, the alumina ceramic, the zinc oxide ceramic and the silicon nitride ceramic are powder with uniform fineness of 80 nm;
the polyurethane resin system includes: 40 parts of isocyanate-terminated polyurethane prepolymer, 5 parts of modified graphene, 5 parts of polyamide resin and 10 parts of triethylene tetramine; the preparation method of the modified graphene comprises the following steps: mixing carboxylated graphene and acetone according to the mass ratio of 1:8, adding diethyl toluene diamine, mixing, raising the temperature to 140 ℃, reacting for 2 hours, drying under reduced pressure, and washing residues with ethanol for 2 times to obtain modified graphene; the dosage of the diethyl toluene diamine is 6 times of the mass of the carboxylated graphene.
The preparation method of the non-stick pan coating based on the interpenetrating network structure comprises the following steps:
(1) preparation of the epoxy resin system:
uniformly mixing an alicyclic epoxy compound, a glycidyl amine type resin, polyethylene wax and pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hydroxyhydrocinnamate) according to the mass ratio, sequentially adding modified carbon fibers, zirconia ceramics, alumina ceramics, zinc oxide ceramics and silicon nitride ceramics, and uniformly stirring for later use;
(2) preparation of polyurethane resin system:
uniformly mixing the isocyanate-terminated polyurethane prepolymer, the modified graphene, the polyamide resin and the triethylene tetramine, and homogenizing under high pressure for later use;
(3) mixing and spraying an epoxy resin system and a polyurethane resin system according to a mass ratio, and heating to 160 ℃ for curing.
To verify the effect of the invention, the following comparative examples were set up:
| comparative example 1 | The difference from example 1 is that the modified carbon fibers used were replaced with carboxylated carbon fibers; |
| comparative example 2 | The difference from example 1 is that the carbon fibers were not pretreated; |
| comparative example 3 | The difference from example 1 is that the isocyanate-terminated polyurethane prepolymer in the polyurethane resin system was replaced with an epoxy resin to form a non-interpenetrating network structure. |
Test examples
Respectively manufacturing a non-stick pan by using a stainless steel pan as a substrate according to the coating schemes of the examples 1-3 and the comparative examples 1-3; and repeating 10 times for each group of non-stick pans, and calculating the average value of the experimental data during the experiment to obtain the final experimental result. Heating each group of non-stick pans to 330 ℃ at a heating rate of 13 ℃/min, and recording the maximum times of repeated heating and cooling under the condition of stable non-stick pan coating; and (3) detecting the wear resistance of each group of non-stick pans by adopting a standard GB/T1768-2006.
The experimental results are as follows:
| repeated heating and cooling times (times) | Abrasion resistance (g) | |
| Example 1 | 6412.57 | 0.0005 |
| Example 2 | 6485.90 | 0.0007 |
| Example 3 | 6512.71 | 0.0005 |
| Comparative example 1 | 4461.17 | 0.0012 |
| Comparative example 2 | 4400.22 | 0.0015 |
| Comparative example 3 | 4208.76 | 0.0018 |
As can be seen from the table, the non-stick pan coating prepared by the method has better durability, is suitable for high-temperature treatment of kitchen cooking and has excellent practicability when the temperature is repeatedly increased and decreased for more than 6412.57 times and the wear resistance is lower than 0.0005 g.
Claims (10)
1. The non-stick pan coating based on the interpenetrating network structure is characterized by being formed by mixing an epoxy resin system and a polyurethane resin system according to a mass ratio of 5-7: 2-3; the epoxy resin system comprises the following components in parts by mass: 30-50 parts of alicyclic epoxy compound, 80-90 parts of glycidyl amine type resin, 3-5 parts of modified carbon fiber, 2-5 parts of pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hydroxyhydrocinnamate), 3-5 parts of zirconia ceramic, 11-12 parts of alumina ceramic, 10-15 parts of zinc oxide ceramic, 13-17 parts of silicon nitride ceramic and 2-5 parts of polyethylene wax;
the polyurethane resin system includes: 35-40 parts of isocyanate-terminated polyurethane prepolymer, 3-5 parts of modified graphene, 5-8 parts of polyamide resin and 10-18 parts of triethylene tetramine.
2. The non-stick pan coating based on the interpenetrating network structure of claim 1, wherein the modified carbon fiber is prepared by the following steps: mixing pyromellitic dianhydride and ethylenediamine according to a molar mass ratio of 2:3-5, pouring into a reaction container, adding quinoline and acetone, uniformly mixing, reacting for 15-19h at 70-80 ℃ in a water bath, putting the pretreated carbon fiber into the solution, and performing ultrasonic treatment for 7-12 min; and centrifuging, washing the carbon fiber with ethanol, and drying to obtain the modified carbon fiber.
3. The non-stick pan coating based on the interpenetrating network structure of claim 1, wherein the modified graphene is prepared by the following steps: mixing the carboxylated graphene and acetone according to the mass ratio of 1:5-8, adding diethyltoluenediamine, mixing, raising the temperature to 140-.
4. The non-stick pan coating based on interpenetrating network structure of claim 1, wherein the zirconia ceramic, alumina ceramic, zinc oxide ceramic, silicon nitride ceramic are powders with uniform fineness of 80-150 nm.
5. The non-stick pan coating based on interpenetrating network structure of claim 2, wherein the quinoline is used in an amount of 1-3% by mass of pyromellitic dianhydride.
6. The non-stick pan coating based on interpenetrating network structure of claim 2, wherein the amount of acetone is 8-10 times the mass of pyromellitic dianhydride.
7. The non-stick pan coating based on interpenetrating network structure of claim 2, wherein the pretreatment of the carbon fibers is: heating the carbon fiber to 800-.
8. The non-stick pan coating based on interpenetrating network structure of claim 2, wherein the amount of the carbon fiber is 45-65% of the mass of the pyromellitic dianhydride.
9. The non-stick pan coating based on interpenetrating network structure of claim 3, wherein the amount of diethyltoluenediamine is 4-6 times the mass of the carboxylated graphene.
10. The method for preparing the non-stick pan coating based on the interpenetrating network structure according to claim 1, comprising:
(1) preparation of the epoxy resin system:
uniformly mixing an alicyclic epoxy compound, a glycidyl amine type resin, polyethylene wax and pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hydroxyhydrocinnamate) according to the mass ratio, sequentially adding modified carbon fibers, zirconia ceramics, alumina ceramics, zinc oxide ceramics and silicon nitride ceramics, and uniformly stirring for later use;
(2) preparation of polyurethane resin system:
uniformly mixing the isocyanate-terminated polyurethane prepolymer, the modified graphene, the polyamide resin and the triethylene tetramine, and homogenizing under high pressure for later use;
(3) mixing and spraying the epoxy resin system and the polyurethane resin system according to the mass ratio, and heating to 150-170 ℃ for curing.
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