CN113736346B - Epoxy resin-based coating material and preparation method and application thereof - Google Patents
Epoxy resin-based coating material and preparation method and application thereof Download PDFInfo
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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Abstract
The application discloses an epoxy resin-based coating material and a preparation method and application thereof, belonging to the technical field of coating materials for marine environments. The epoxy resin-based coating material comprises the following components in parts by weight: 60-90 parts of epoxy resin, 5-15 parts of nano composition filler, 0.01-3 parts of coupling agent and 5-40 parts of curing agent; wherein the nano composition filler comprises (1-6) by weight: (3-9) first and second nanoparticles selected from one of nano silver, nano doped zinc oxide, nano aluminum and nano copper, respectively, the first and second nanoparticles being different from the second nanoparticles. The epoxy resin-based coating material has high toughness and low surface free energy, can be used as a coating material for metal surfaces in marine environments, prevents dirt from being deposited on the surfaces of the coatings, and has an excellent corrosion resistance effect.
Description
Technical Field
The application relates to an epoxy resin-based coating material and a preparation method and application thereof, belonging to the technical field of coating materials for marine environments.
Background
The marine environment has a large amount of corrosive and polluting ions, such as Cl-，Mg2+，Ca2+，SO4 2-And HCO3 -Therefore, metal pipelines and ships in seawater inevitably suffer from serious scaling and corrosion predicament in the using process, corrosion and scaling phenomena often occur simultaneously and act synergistically, and local corrosion is often caused by serious scaling, so that the service lives of the pipelines and the ships are shortened, the production efficiency is reduced, and the production cost is increased. Therefore, the scaling problem and the corrosion problem of the metal surface in the marine environment are two major problems which need to be solved urgently at present.
The epoxy resin is a common thermosetting resin, has excellent physical property and adhesive property, convenient operation process, flexible curing process, good chemical corrosion resistance and mould resistance of cured products, and can be widely applied to the national economic fields of coatings, adhesives, composite material matrixes, compression molding forming materials and the like. However, the epoxy resin cured product has the defects of high crosslinking degree, high brittleness, easy cracking and the like, and simultaneously, because the structure of the epoxy resin cured product contains a large amount of polar groups such as hydroxyl, amino, ester, ether bond, uncured epoxy group and the like, the epoxy resin cured product has high surface free energy, is easy to be adhered by pollutants, is very unfavorable for the anti-scaling and anti-corrosion performances of the epoxy resin cured product, and has poor toughness, so that the application of the epoxy resin cured product as a coating and an adhesive in a marine environment is limited. Therefore, the epoxy resin-based material needs to be improved to be more widely applied to marine environments.
Disclosure of Invention
In order to solve the problems, the epoxy resin-based coating material has high toughness and low surface free energy, can be used as a coating material of a metal surface in a marine environment, prevents dirt from being deposited on the surface of the coating, and has an excellent corrosion resistance effect.
According to one aspect of the present application, there is provided an epoxy resin based coating material comprising, in parts by weight: 60-90 parts of epoxy resin, 5-15 parts of nano composition filler, 0.01-3 parts of coupling agent and 5-40 parts of curing agent;
wherein the nano composition filler comprises (1-6) by weight: (3-9) first and second nanoparticles selected from at least one of nano silver, nano doped zinc oxide, nano aluminum and nano copper, respectively, the first and second nanoparticles being different from the second nanoparticle.
Preferably, the epoxy resin-based coating material comprises: 70-80 parts of epoxy resin, 8-12 parts of nano composition filler, 0.5-2 parts of coupling agent and 15-30 parts of curing agent;
more preferably, the epoxy resin-based coating material includes: 75 parts of epoxy resin, 10 parts of nano composition filler, 0.97 part of coupling agent and 20 parts of curing agent.
By selecting the composition of the epoxy resin coating material, the epoxy resin coating material has good curing performance, bonding strength and anti-scaling performance.
Optionally, the nano-composition filler comprises 1 to 3 parts by weight of nano silver, 2 to 6 parts by weight of nano doped zinc oxide and 2 to 6 parts by weight of nano aluminum,
wherein, the doping element in the nano-doped zinc oxide is at least one of manganese, nickel, cobalt and iron;
the coating material also comprises 2 to 5 parts of curing accelerator, preferably 3 to 4 parts, and more preferably 3.5 parts.
Preferably, the nano-composition filler comprises 2 parts of nano silver, 4 parts of nano doped zinc oxide and 4 parts of nano aluminum,
wherein, the doping element in the nano-doped zinc oxide is nickel.
Optionally, the weight percentage of the doping element in the nano-doped zinc oxide is 10% to 20%, preferably 15%.
Due to the existence of the doping elements, the modified coating material has more excellent electrochemical characteristics, and further the corrosion resistance of the metal surface is further enhanced.
Optionally, the nano-composite filler is a nano-composite filler after plasma irradiation, and the gas of the plasma irradiation is O2、Ar、NH3And CO2At least one of (1).
Preferably, the plasma irradiation gas is Ar and NH3The mixed gas of (1).
More preferably, the plasma irradiation gas has a volume flow ratio of (0.5-1.5): ar and NH of (7-11)3Preferably 1: 9.
by selecting the gas type and volume flow ratio of plasma irradiation, different types and contents of polar groups can be introduced, so that active substances in a metastable state structure are generated on the surface of the metal nano particle, the active substances are favorable for being combined with epoxy resin, the nano particle is ensured to better exert the characteristics of the epoxy resin-based coating material, and the toughness of the epoxy resin-based coating material is improved.
Optionally, the particle size of the nano silver D50 is 10nm-50nm, preferably 10 nm-30 nm, and more preferably 20 nm;
the D50 particle size of the nano-doped zinc oxide is 10nm-50nm, preferably 10 nm-30 nm, and more preferably 20 nm;
the D50 particle size of the nano aluminum is 10nm-50nm, preferably 10 nm-30 nm, and more preferably 20 nm;
the D50 particle size of the nano copper is 10nm-50nm, preferably 10 nm-30 nm, and more preferably 20 nm.
By controlling the particle size of the nanoparticles, the mixing manufacturability and the exertion of the nano effect can be fully balanced. On one hand, the particle size is too small, and the dispersion difficulty of the nano particles in the epoxy resin is higher; on the other hand, the larger the particle size, the worse the nano-size effect, and the inferior overall performance.
Optionally, the epoxy resin is at least one of bisphenol a epoxy resin, bisphenol F epoxy resin, tetraglycidyl xylene diamine, tetraglycidyl diaminodiphenylmethane, m-xylylenediamine tetraglycidyl amine, epoxy novolac resin, epoxy o-cresol novolac resin, triglycidyl p-aminophenol, epoxy chloro resin, epoxy bromo resin, and epoxy fluoro resin;
the curing agent is at least one of a polyether amine curing agent, a phenolic aldehyde amine curing agent, a polyamide curing agent, an alicyclic amine curing agent, an aromatic amine curing agent, an aliphatic amine curing agent and an anhydride curing agent, and preferably is an anhydride curing agent;
the curing accelerator is at least one of a modified imidazole accelerator, a modified amine accelerator, a boron trifluoride-amine complex, an organic urea accelerator and a tertiary amine accelerator, and is preferably a tertiary amine accelerator;
the coupling agent is at least one of silane coupling agent, titanate coupling agent and chromium complex coupling agent;
preferably, the epoxy resin is bisphenol a epoxy resin, the curing agent is methyl hexahydrophthalic anhydride, the accelerator is 2,4, 6-tris (dimethylaminomethyl) phenol, and the coupling agent is a silane coupling agent.
According to another aspect of the present application, there is provided a method for preparing the epoxy-based coating material according to any one of the above, comprising the steps of:
irradiating the nano composition filler by plasma to obtain an irradiated nano composition filler; and mixing the irradiated nano composition filler with the epoxy resin, the coupling agent and the curing agent to obtain the epoxy resin-based coating material.
Optionally, the plasma-irradiated gas is O2、Ar、NH3And CO2Preferably a volume flow ratio of 1:9 Ar and NH3(ii) a The power of the plasma irradiation is 50W-500W, preferably 100W-300W, and more preferably 150W;
the time of plasma irradiation is 0.5min-15min, preferably 5min-13min, preferably 10 min.
By controlling the plasma irradiation condition and the type and concentration of plasma gas, the combination state of the nano particles and the epoxy resin is optimized, and the toughness and the hydrophobicity of the epoxy resin-based coating material are ensured.
Optionally, adding the coupling agent into the epoxy resin, then adding the irradiated nano composition filler into the epoxy resin, and grinding to obtain nano composition filler-epoxy resin slurry;
and adding an accelerator and the curing agent into the nano composition filler-epoxy resin slurry, and mixing to obtain the epoxy resin-based coating material.
Optionally, the irradiated nano-composition filler is added to the epoxy resin under the action of ultrasound.
And optionally grinding for 1-3 times by a three-roll grinder to obtain the nano-composition filler-epoxy resin slurry.
According to yet another aspect of the present application, there is provided an epoxy-based coating processed from an epoxy-based coating material;
wherein the epoxy resin-based coating material is the coating material or the coating material prepared by the method.
According to a further aspect of the present application there is provided the use of an epoxy-based coating as described above in a metal pipe or vessel in the ocean.
Benefits of the present application include, but are not limited to:
1. according to the epoxy resin-based coating material, the nano composition filler is added to serve as a zero-dimensional nano material between a bulk material and molecules, so that an interaction force can be generated between the nano composition filler and groups such as hydroxyl groups and epoxy groups on the epoxy resin, a stable structure is obtained, the toughness of the epoxy resin can be effectively improved, the surface free energy of the epoxy resin can be reduced, and the hydrophobic epoxy resin-based coating material is obtained; the epoxy resin-based coating material can be used as a coating material for metal surfaces in marine environments, prevents dirt from being deposited on the surfaces of the coatings, and has an excellent corrosion resistance effect.
2. According to the epoxy resin-based coating material, through selecting the proper composition and adding amount of the nano composition filler, the synergistic effect among various nano particles is ensured, the good compatibility among various nano particles is ensured, the compatibility between the nano composition filler and the epoxy resin is also better, and the toughness and the hydrophobicity of the coating material are further improved.
3. According to the preparation method of the epoxy resin-based coating material, due to the fact that the compatibility among multiple nano particles is poor and the nano particles are difficult to mix uniformly, the surface of the nano particles is treated by the plasma gas, the roughness of the surfaces of the nano particles can be improved, the bonding capacity between the nano particles and epoxy resin is stronger, the compatibility among nano composition fillers can be improved, the multiple nano particles can be mixed uniformly, and the toughness and the hydrophobicity of the epoxy resin-based coating material are further enhanced.
4. According to the preparation method of the epoxy resin-based coating material, proper plasma gas and plasma treatment conditions are selected according to the type and the addition amount of the nano particles, the addition sequence of each component is controlled, and the binding capacity between the nano composition filler and the epoxy resin is further improved.
5. The epoxy resin-based coating has excellent anti-scaling capability and corrosion resistance as a metal surface coating, can remarkably prolong the service life of a ship or a metal pipeline as a surface coating of the ship or the metal pipeline in a marine environment, and saves production cost.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the raw materials and catalysts in the examples of the present application were all purchased commercially.
Example 1 coating Material 1#
The preparation steps of the epoxy resin-based coating material No. 1 are as follows:
s1: uniformly mixing 2.0 parts of nano silver, 4.0 parts of nano doped zinc oxide and 4.0 parts of nano aluminum to form nano composition filler, and subjecting the nano composition filler to Ar and NH under 150W discharge power3(volume flow ratio is 1: 9) irradiating the plasma for 10min to obtain irradiated nano composition filler, wherein the grain diameter of D50 of nano silver is 20 nm, the grain diameter of D50 of nano doped zinc oxide is 20 nm, the grain diameter of D50 of nano aluminum is 20 nm, and the nano doped zinc oxide is doped with 15% (weight percentage) of nickel element;
s2: adding 0.97 part of silane coupling agent into 75.0 parts of bisphenol A type epoxy resin;
s3: under the ultrasonic action of 26.5kHz frequency, adding the irradiated nano composition filler obtained by S1 into the epoxy resin prepared by S2, and then grinding for 3 times by a three-roll grinder to obtain nano composition filler-epoxy resin slurry;
s4: and adding 20.0 parts of methylhexahydrophthalic anhydride and 3.5 parts of 2,4, 6-tris (dimethylaminomethyl) phenol into the nano composition filler-epoxy resin slurry obtained in S3, uniformly mixing, and curing for 480 min to obtain the epoxy resin-based coating material No. 1.
Example 2 coating Material 2#
The preparation steps of the epoxy resin-based coating material No. 2 are as follows:
s1: uniformly mixing 2.0 parts of nano silver, 4.0 parts of nano doped zinc oxide and 4.0 parts of nano aluminum to form a nano composition filler, wherein the D50 particle size of the nano silver is 20 nm, the D50 particle size of the nano doped zinc oxide is 20 nm, and the D50 particle size of the nano aluminum is 20 nm;
s2: adding 0.97 part of silane coupling agent into 75.0 parts of bisphenol A type epoxy resin;
s3: under the ultrasonic action of 26.5kHz frequency, adding the nano composition filler obtained from S1 into the epoxy resin prepared from S2, and then grinding for 3 times by a three-roll grinder to obtain nano composition filler-epoxy resin slurry;
s4: and adding 20.0 parts of methylhexahydrophthalic anhydride and 3.5 parts of 2,4, 6-tris (dimethylaminomethyl) phenol into the nano composition filler-epoxy resin slurry obtained in S3, uniformly mixing, and curing for 480 min to obtain the epoxy resin-based coating material No. 2.
Example 3 coating Material 3#
Example 3 is different from example 1 in that, in S1, 4.0 parts of nano silver, 3.0 parts of nano-doped zinc oxide and 3.0 parts of nano aluminum are uniformly mixed to form a nano composition filler, and the nano composition filler is subjected to Ar and NH at a discharge power of 150W3(volume flow ratio is 1: 9) irradiating the plasma for 10min to obtain the irradiated nano composition filler;
the remaining conditions were the same as in example 1, and epoxy resin-based coating material # 3 was obtained.
Example 4 coating Material 4#
Example 4 is different from example 1 in that, in S1, 2.0 parts of nano silver and 8.0 parts of nano aluminum are uniformly mixed to form a nano composition filler, and the nano composition filler is subjected to Ar and NH under 150W discharge power3(volume flow ratio is 1: 9) irradiating the plasma for 10min to obtain the irradiated nano composition filler;
the rest of the conditions were the same as in example 1, and epoxy resin-based coating material # 4 was obtained.
Example 5 coating Material 5#
Example 5 is different from example 1 in that, in S1, 3.0 parts of nano silver and 7.0 parts of nano-doped zinc oxide are uniformly mixed to form a nano-composite filler, and the nano-composite filler is subjected to Ar and NH at a discharge power of 150W3(volume flow ratio is 1: 9) irradiating the plasma for 10min to obtain the irradiated nano composition filler;
the remaining conditions were the same as in example 1, and epoxy resin-based coating material # 5 was obtained.
Example 6 coating Material 6#
Example 6 is different from example 1 in that, in S1, 5.0 parts of nano-doped zinc oxide and 8.0 parts of nano-aluminum are uniformly mixed to form a nano-composite filler, and the nano-composite filler is subjected to Ar and NH at a discharge power of 150W3(volume flow ratio is 1: 9) irradiating the plasma for 10min to obtain the irradiated nano composition filler;
the remaining conditions were the same as in example 1, and epoxy resin-based coating material # 6 was obtained.
Example 7 coating Material 7#
Example 7 is different from example 1 in that, in S1, 2.0 parts of nano silver, 4.0 parts of nano-doped zinc oxide and 4.0 parts of nano aluminum are uniformly mixed to form a nano-composite filler, and the nano-composite filler is subjected to O at a discharge power of 150W2And NH3(volume flow ratio is 1: 9) irradiating the plasma for 10min to obtain the irradiated nano composition filler;
the remaining conditions were the same as in example 1, and epoxy resin-based coating material # 7 was obtained.
Example 8 coating Material 8#
Example 8 is different from example 1 in that, in S1, 2.0 parts of nano silver, 4.0 parts of nano-doped zinc oxide and 4.0 parts of nano aluminum are uniformly mixed to form a nano composition filler, and the nano composition filler is subjected to Ar and NH at a discharge power of 150W3(the volume flow ratio is 1.5: 8.5) irradiating the plasma for 10min to obtain the irradiated nano composition filler;
the rest of the conditions were the same as in example 1, and epoxy resin-based coating material # 8 was obtained.
Example 9 coating Material 9#
Example 9 is different from example 1 in that, in S1, 2.0 parts of nano silver, 4.0 parts of nano-doped zinc oxide and 4.0 parts of nano aluminum are uniformly mixed to form a nano composition filler, and the nano composition filler is subjected to Ar and N under 150W discharge power2(volume flow ratio is 1: 9) irradiating the plasma for 10min to obtain the irradiated nano composition filler;
the remaining conditions were the same as in example 1, and epoxy resin-based coating material # 9 was obtained.
Example 10 coating Material 10#
Example 10 is different from example 1 in that, in S1, 2.0 parts of nano silver, 4.0 parts of nano-doped zinc oxide and 4.0 parts of nano aluminum are uniformly mixed to form a nano composition filler, and the nano composition filler is subjected to Ar and NH at a discharge power of 100W3(volume flow ratio is 1: 9) irradiating the plasma for 5min to obtain irradiated nano composition filler;
the remaining conditions were the same as in example 1, and epoxy resin-based coating material # 10 was obtained.
Example 11 coating Material 11#
Example 11 is different from example 1 in that, in S1, 2.0 parts of nano silver, 4.0 parts of nano-doped zinc oxide and 4.0 parts of nano aluminum are uniformly mixed to form a nano composition filler, and the nano composition filler is subjected to Ar and NH at a discharge power of 700W3(volume flow ratio is 1: 9) irradiating the plasma for 5min to obtain irradiated nano composition filler;
the remaining conditions were the same as in example 1, and epoxy resin-based coating material # 11 was obtained.
Example 12 coating Material 12#
Example 12 differs from example 1 in that in S2, 0.97 parts of a silane coupling agent was added to 75.0 parts of tetraglycidyl xylene diamine;
the remaining conditions were the same as in example 1, and epoxy resin-based coating material # 12 was obtained.
Example 13 coating Material 13#
Example 13 is different from example 1 in that, in S4, 20.0 parts of diaminodiphenylmethane and 3.5 parts of 2-ethyl-4-methylimidazole are added to the nanocomposite filler-epoxy resin slurry obtained in S3, and after uniform mixing, the epoxy resin-based coating material # 13 is obtained after 480 min of curing;
the remaining conditions were the same as in example 1.
Example 14 coating Material 14#
Example 14 is different from example 1 in that 20.0 parts of methylhexahydrophthalic anhydride was added to the nanocomposite filler-epoxy resin slurry obtained in S3 in S4, and after uniform mixing, the mixture was cured for 480 min to obtain epoxy resin-based coating material # 14;
the remaining conditions were the same as in example 1.
Comparative example 1 coating Material D1#
Comparative example 1 is different from example 1 in that, in S1, 10.0 parts of nano aluminum are uniformly mixed to form a nano composition filler, and the nano composition filler is subjected to Ar and NH at a discharge power of 150W3(volume flow ratio is 1: 9) irradiating the plasma for 10min to obtain the irradiated nano composition filler;
the remaining conditions were the same as in example 1, to obtain epoxy resin-based coating material D1 #.
Comparative example 2 coating Material D2#
Comparative example 2 is different from example 1 in that, in S1, 2.0 parts of nano silver, 4.0 parts of nano zinc and 4.0 parts of nano aluminum are uniformly mixed to form a nano composition filler, and the nano composition filler is subjected to Ar and NH at a discharge power of 150W3(the volume flow ratio is 1: 9) irradiating the plasma for 10min to obtain the irradiated nano composition filler, wherein the D50 particle size of the nano zinc is 20 nm;
the remaining conditions were the same as in example 1, to obtain epoxy resin-based coating material D2 #.
Comparative example 3 coating Material D3#
Comparative example 3 is different from example 1 in that, in S1, 2.0 parts of nano silver, 4.0 parts of nano-doped zinc oxide and 4.0 parts of nano-iron oxide were uniformly mixed to form a nano-composite filler, and the nano-composite filler was subjected to Ar and NH at a discharge power of 150W3(the volume flow ratio is 1: 9) irradiating the plasma for 10min to obtain the irradiated nano composition filler, wherein the D50 particle size of the nano iron oxide is 20 nm;
the remaining conditions were the same as in example 1, to obtain epoxy resin-based coating material D3 #.
Comparative example 4 coating Material D4#
Comparative example 4 is different from example 1 in that, in S1, 5.0 parts of nano silver, 12.0 parts of nano-doped zinc oxide and 4.0 parts of nano aluminum were uniformly mixed to form a nano composition filler, and the nano composition filler was subjected to Ar and NH at a discharge power of 150W3(volume flow ratio is 1: 9) irradiating the plasma for 10min to obtain the irradiated nano composition filler;
the remaining conditions were the same as in example 1, to obtain epoxy resin-based coating material D4 #.
Comparative example 5 coating Material D5#
Comparative example 5 is different from example 1 in that 0.97 parts of a silane coupling agent was added to 110.0 parts of bisphenol a type epoxy resin in S2;
the remaining conditions were the same as in example 1, to obtain epoxy resin-based coating material D5 #.
Examples of the experiments
After casting were performed on the coating materials 1# -14# and D1# -D5# obtained in examples 1-14 and comparative examples 1-5, respectively, notched impact strength test by a static contact angle tester was performed, as described below, and the test results are shown in table 1.
And (3) casting body manufacturing process: and (3) pumping bubbles from the coating material in a vacuum oven, pouring the coating material into a mould after no obvious bubbles are generated, and curing according to the existing curing process.
Water static contact angle test: and dripping a drop of water on the surface of the casting body, photographing a balance system after a solid-liquid-gas three-phase interface is balanced, and measuring a contact angle by using a full-automatic contact angle measuring instrument.
Notched impact strength test: the samples were tested for notched Izod impact strength according to GB/T1843-2008.
TABLE 1
| Numbering | Water static contact Angle (°) | Notched impact strength (J/m) |
| Material 1# | 177 | 31.5 |
| Material 2# | 132 | 14.3 |
| Material No. 3 | 158 | 19.7 |
| Material 4# | 155 | 17.6 |
| Material 5# | 159 | 18.5 |
| Material 6# | 148 | 17.1 |
| Material 7# | 161 | 20.3 |
| Material 8# | 155 | 29.2 |
| Material 9# | 127 | 13.8 |
| Material 10# | 157 | 18.6 |
| Material 11# | 136 | 12.9 |
| Material 12# | 151 | 18.7 |
| Material 13# | 160 | 17.5 |
| Material 14# | 153 | 19.1 |
| MaterialD1# | 119 | 12.1 |
| Material D2# | 121 | 11.6 |
| Material D3# | 117 | 12.8 |
| Material D4# | 129 | 10.7 |
| Material D5# | 126 | 11.9 |
As can be seen from table 1, the coating material of the present application can reduce the surface free energy of the epoxy resin, improve the hydrophobicity of the coating material, and make the coating material have higher toughness by adding the nano composition filler.
The coating materials 1# -14# and D1# -D5# obtained in examples 1-14 and comparative examples 1-5 were coated on a copper plate, respectively, to obtain coatings 1# -14# and D1# -D5#, which were tested for their bonding strength, anti-scaling ability and anti-corrosion ability, as described below, and the test results are shown in Table 2.
Bonding strength: the binding strength between the coating and the substrate was determined with reference to the GB/T8642-2002 standard.
Scale formation amount: a sealed constant-temperature water bath is used as a scaling test instrument, metal sheets with the same area are weighed and placed in the water bath, the scaling test time is set to be 72h, a scaled sample is taken out, and the sample is processed and weighed to obtain the scaling amount.
Corrosion rate: the corrosion resistance of the metals and their coatings was tested according to the GB/T10125-.
TABLE 2
| Numbering | Bonding Strength (MPa) | Amount of scale formation (mg) | Corrosion rate (g/m 2) |
| Coating No. 1 | 82.5 | 3.0 | 2.0 |
| Coating No. 2 | 50.8 | 12.4 | 8.7 |
| Coating No. 3 | 72.4 | 6.2 | 3.1 |
| Coating 4# | 69.8 | 6.5 | 3.7 |
| Coating 5# | 75.6 | 4.9 | 2.6 |
| Coating No. 6 | 77.1 | 3.9 | 2.3 |
| Coating 7# | 73.9 | 4.1 | 3.2 |
| Coating No. 8 | 69.8 | 6.1 | 4.1 |
| Coating 9# | 61.4 | 11.9 | 6.9 |
| Coating 10# | 78.0 | 3.7 | 2.8 |
| Coating 11# | 62.2 | 13.8 | 9.4 |
| Coating No. 12 | 77.4 | 4.1 | 3.4 |
| Coating 13# | 78.8 | 3.9 | 2.2 |
| Coating 14# | 76.4 | 4.2 | 3.2 |
| Coating D1# | 54.3 | 12.4 | 7.1 |
| Coating D2# | 57.1 | 11.8 | 5.3 |
| Coating D3# | 49.8 | 13.9 | 7.9 |
| Coating D4# | 53.9 | 11.7 | 6.1 |
| Coating D5# | 58.2 | 12.8 | 6.8 |
As can be seen from Table 2, the coating can be tightly combined with a matrix, and has excellent anti-scaling capability and corrosion resistance, so that the coating can be used as a coating of ships or metal pipelines in marine environment, the service life is prolonged, and the production cost is saved.
The above description is only an example of the present application, and the protection scope of the present application is not limited by these specific examples, but is defined by the claims of the present application. Various modifications and changes may occur to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the technical idea and principle of the present application should be included in the protection scope of the present application.
Claims (9)
1. An epoxy resin-based coating material is characterized by comprising the following components in parts by weight: 60-90 parts of epoxy resin, 5-15 parts of nano composition filler, 0.01-3 parts of coupling agent and 5-40 parts of curing agent;
wherein the nano composition filler comprises (1-6) by weight: (3-9) first and second nanoparticles selected from at least one of nano silver, nano doped zinc oxide, nano aluminum and nano copper, respectively, the first and second nanoparticles being different;
the nano composition filler is a nano composition filler subjected to plasma irradiation, and the gas irradiated by the plasma is O2、Ar、NH3And CO2At least one of (1).
2. The coating material of claim 1, wherein the nano-composition filler comprises, in parts by weight, 1 to 3 parts of nano-silver, 2 to 6 parts of nano-doped zinc oxide, and 2 to 6 parts of nano-aluminum,
wherein, the doping element in the nano-doped zinc oxide is at least one of manganese, nickel, cobalt and iron;
the coating material also comprises 2-5 parts of a curing accelerator.
3. The coating material according to claim 1 or 2, wherein the nanosilver has a D50 particle size of 10nm to 50 nm;
the D50 particle size of the nano-doped zinc oxide is 10nm-50 nm;
the D50 particle size of the nano aluminum is 10nm-50 nm;
the D50 particle size of the nano copper is 10nm-50 nm.
4. The coating material of claim 2, wherein the epoxy resin is at least one of bisphenol a epoxy resin, bisphenol F epoxy resin, tetraglycidyl xylenediamine, tetraglycidyl diaminodiphenylmethane, m-xylylenediamine tetraglycidyl amine, epoxy novolac, epoxy ortho-cresol novolac, triglycidyl-p-aminophenol, epoxy chloro-epoxy resin, epoxy bromo-epoxy resin, and epoxy fluoro-epoxy resin;
the curing agent is at least one of a polyether amine curing agent, a phenolic aldehyde amine curing agent, a polyamide curing agent, an alicyclic amine curing agent, an aromatic amine curing agent, an aliphatic amine curing agent and an anhydride curing agent;
the curing accelerator is at least one of modified imidazole accelerators, modified amine accelerators, boron trifluoride-amine complexes, organic urea accelerators and tertiary amine accelerators;
the coupling agent is at least one of silane coupling agent, titanate coupling agent and chromium complex coupling agent.
5. A process for the preparation of the epoxy resin based coating material according to any of claims 1-4, characterized in that it comprises the following steps:
irradiating the nano composition filler by plasma to obtain an irradiated nano composition filler; and mixing the irradiated nano composition filler with the epoxy resin, the coupling agent and the curing agent to obtain the epoxy resin-based coating material.
6. The method of claim 5, wherein the plasma-irradiated gas is O2、Ar、NH3And CO2At least one of;
the power of the plasma irradiation is 50W-500W;
the plasma irradiation time is 0.5min-15 min.
7. The method of claim 5 or 6, wherein the coupling agent is added to the epoxy resin, and then the irradiated nano-composition filler is added to the epoxy resin, and the nano-composition filler-epoxy resin slurry is obtained after grinding;
and adding an accelerator and the curing agent into the nano composition filler-epoxy resin slurry, and mixing to obtain the epoxy resin-based coating material.
8. The epoxy resin-based coating is characterized in that the epoxy resin-based coating is prepared by processing an epoxy resin-based coating material;
wherein the epoxy resin-based coating material is the coating material of any one of claims 1 to 4 or the coating material prepared by the method of any one of claims 5 to 7.
9. Use of the epoxy-based coating according to claim 8 in metal pipelines or ships in the sea.
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| WO2004092250A1 (en) * | 2003-04-15 | 2004-10-28 | Biogenon Ltd. | Biocompatible material |
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| DE10252421A1 (en) * | 2002-11-12 | 2004-05-19 | Bayer Ag | Coating system, e.g. for polycarbonate panels or lenses, has an abrasion-resistant layer containing a silane-based polycondensate and a topcoat based on epoxyalkyl-silane and hydrolysable metal compounds |
| JP5064649B2 (en) * | 2003-08-28 | 2012-10-31 | 大日本印刷株式会社 | Anti-reflection laminate |
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| WO2004092250A1 (en) * | 2003-04-15 | 2004-10-28 | Biogenon Ltd. | Biocompatible material |
| CN103025516A (en) * | 2010-07-22 | 2013-04-03 | 费罗公司 | Hermetically sealed electronic device using coated glass flakes |
| CN109266167A (en) * | 2018-08-29 | 2019-01-25 | 佛山市三水固丽雅五金装饰材料有限公司 | A kind of high temperature resistant low temperature curing type multifunctional epoxide polyester powder coating and preparation method thereof |
| CN110643267A (en) * | 2019-11-11 | 2020-01-03 | 厦门双瑞船舶涂料有限公司 | Thin-coating heavy-duty anticorrosive coating and preparation method thereof |
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Denomination of invention: A kind of epoxy resin-based coating material and preparation method and application thereof Effective date of registration: 20220831 Granted publication date: 20220215 Pledgee: Pingyuan County sub branch of Postal Savings Bank of China Ltd. Pledgor: Shandong Jiangshan Fiber Technology Co.,Ltd. Registration number: Y2022980014105 |