CN113278338A

CN113278338A - High-toughness low-energy-consumption graphene biological-based heavy-duty anticorrosive coating and preparation method thereof

Info

Publication number: CN113278338A
Application number: CN202110466627.6A
Authority: CN
Inventors: 赵韵飞; 殷立平; 赵绍洪
Original assignee: Changzhou Guanghui New Material Research Institute Co ltd
Current assignee: Changzhou Guanghui New Material Research Institute Co ltd
Priority date: 2021-04-28
Filing date: 2021-04-28
Publication date: 2021-08-20

Abstract

The invention belongs to the technical field of coatings, and particularly relates to a high-toughness low-energy-consumption graphene biological basis weight anticorrosive coating and a preparation method thereof. The coating consists of a component A and a component B, and the coating comprises the following components in percentage by weight: the component A comprises 30-45% of modified phenolic resin, 0.5-0.8% of defoaming agent, 0.1-0.3% of base material wetting agent, 0.5-1.0% of hyperbranched coupling agent, 22-35% of iron oxide red powder, 2.5-8% of zinc phosphate, 5-10% of shell pearl layer, 2-5% of modified graphene oxide solution, 2-5% of hollow glass microsphere, 0.2-1.0% of flatting agent and the balance of diluent. Firstly, preparing a modified graphene oxide solution and modified phenolic resin; and preparing the heavy anti-corrosion coating. The heavy-duty anticorrosive coating prepared by the invention has outstanding anticorrosive and heat-insulating properties, high toughness and low energy consumption.

Description

High-toughness low-energy-consumption graphene biological-based heavy-duty anticorrosive coating and preparation method thereof

Technical Field

The invention belongs to the field of coatings, and particularly relates to a high-toughness low-energy-consumption graphene biological basis weight anticorrosive coating and a preparation method thereof.

Background

Corrosion of metal products and equipment, large platforms, etc. is a common phenomenon due to chemical action in climatic environments. The corrosion prevention is usually non-metal protection, corrosion-resistant metal protection, electrochemical protection, corrosion inhibitor addition and the like. While most paint protection is non-metallic. The coating of the coating film is relatively economical, practical and convenient in several treatment modes. In harsh environments, the requirements on the coating are very high.

Common heavy duty anticorrosion systems include epoxy, chlorinated rubber, polyurethane, solvent-free high solids, and the like. The coating thickness is substantially over 200-300 microns, and even over one or two thousand microns. The performance varies widely. The environmental friendliness is generally poor. The performance quality and the environmental protection energy consumption are difficult to balance. The main points are as follows: the tensile strength and the flexibility of a paint film cannot adapt to external changes, the coating can be changed under the high-temperature environment and the like, and the binding force is reduced; the system can not fully exert the capability of resisting corrosion under special harsh conditions; in places difficult to repeatedly construct and maintain, how to reduce the construction period and how to quickly establish an anticorrosive coating is difficult; various kinds of rust-preventive pigments and resins are incompatible and liable to swell, so that there are problems of various degrees of production stability and storage stability. Many times these problems directly affect coating performance.

Patent CN106189719A provides a graphene anticorrosive paint and a preparation method thereof, wherein the graphene anticorrosive paint consists of a component A and a component B, and the weight percentages are as follows: the component A comprises 20-30% of epoxy resin, 1-3% of graphene, 0.5-2% of dispersant, 15-25% of talcum powder, 10-20% of zinc powder and 1-5% of aluminum paste; the component B comprises 30-50% of cashew nut shell oil phenolic amide and 10-30% of polyamide. The graphene anticorrosive paint is simple and convenient in process and stable in storage, has excellent adhesive force on substrates such as steel and iron, but the prepared anticorrosive paint is not environment-friendly, has insufficient coating strength, is not heat-insulating, and has poor flexibility which can not adapt to external changes.

Disclosure of Invention

Aiming at the problems that the heavy-duty anticorrosive coating in the prior art is poor in environmental protection and energy conservation, single in performance, incapable of fully meeting the requirements, insufficient in general toughness of the coating, not suitable for special base planes, inconvenient to operate, multiple in construction way and the like, the heavy-duty anticorrosive coating constructs a heavy-duty anticorrosive system, is outstanding in anticorrosive and heat-insulating performance, and has high toughness and low energy consumption. The purposes of sustainable development and no negative influence on the surrounding environment are achieved.

The invention provides a high-toughness low-energy-consumption graphene biological basis weight anticorrosive coating. The coating consists of a component A and a component B, and the coating comprises the following components in percentage by weight: the component A comprises 30-45% of modified phenolic resin, 0.5-0.8% of defoaming agent, 0.1-0.3% of base material wetting agent, 0.5-1.0% of hyperbranched coupling agent, 22-35% of iron oxide red powder, 2.5-8% of zinc phosphate, 5-10% of shell pearl layer, 2-5% of modified graphene oxide solution, 2-5% of hollow glass microsphere, 0.2-1.0% of flatting agent and the balance of diluent.

Wherein the hyperbranched coupling agent is hyperbranched polyurethane modified silane polymer (Dow Corning), and the diluent is butanol.

The component B comprises 100 parts of alicyclic amine and 0-10 parts of diluent.

Wherein the alicyclic amine is isophorone diamine. The diluent is butanol.

The invention also provides a preparation method of the high-toughness low-energy-consumption graphene biobased heavy-duty anticorrosive coating, which comprises the following specific steps:

preparation of modified graphene oxide solution

(1) Charging graphite into concentrated H₂SO₄: concentrated H₃PO₄9:1, stirring thoroughly, and heating in a water bath at 4 ℃. Slowly adding potassium permanganate into the mixture. The reaction was carried out for half an hour at a bath temperature of 35 ℃. Adding 60 deg.C water. And slowly adding enough hydrogen peroxide (until the solution color is bright yellow, no bubbles are generated) with the mass percent of 5%, reacting at the temperature of 80 ℃ for half an hour, centrifuging and washing the solution, and finally, setting the pH value of a filter cake to be 7. And (4) carrying out ultrasonic treatment and drying for later use.

(2) And ultrasonically dispersing the graphene oxide into 0.5mg/ml aqueous solution. Adding a coupling agent KH570 into the aqueous solution, heating in a water bath at 70 ℃, reacting for 24h, and grafting coupling agent molecules. And (3) after obtaining the modified graphene oxide solution, treating and drying for later use.

(3) Ethanol is added before use, and the modified graphene oxide is ultrasonically dispersed into a 2mg/ml solution.

Preparation of modified phenolic resin

The preparation method comprises the following steps: adding 80-200 parts of lignin into 100 parts of phenol and 150 parts of sodium hydroxide at 60 ℃, stirring for half an hour, adding 130 parts of 37% formaldehyde solution, reacting at 70 ℃ for 2 hours, heating to 90 ℃ and reacting for 1 hour, and adjusting the pH of a product after the reaction to 7-8 to obtain the bio-based phenolic resin; and adding excessive ethylene oxide, and reacting at 120 ℃ for 1h to obtain the modified phenolic resin.

Preparation of three-layer heavy-duty anticorrosive paint

(1) Adding the modified phenolic resin into a batching kettle, adding the defoaming agent, the hyperbranched coupling agent and the wetting agent, and uniformly stirring. Adding the modified graphene oxide solution, the iron oxide red powder, the zinc phosphate and the shell pearl layer while stirring. The slurry was ground to a fineness of 40 microns on a sand mill.

(2) And slowly stirring the ground slurry, adding a flatting agent, a defoaming agent and a diluting agent, and coating 4 cups of the slurry with the viscosity of 40-80 seconds. Then slowly adding the glass hollow micro-beads at a low speed. Obtaining the component A.

(3) Adding a proper amount of diluent into the specified alicyclic amine, and stirring to form the component B.

(4) And (5) testing each index when the ratio of A to B is 5: 1.

Has the advantages that:

(1) the graphene has a special two-dimensional lamellar structure, has a good effect of slowing down the permeation of water, oxygen and ions, and can delay the corrosion process. And its stable sp²The hybrid structure enables it to form a physical barrier between the metal and the active medium, preventing diffusion permeation. This structure can effectively increase the hardness, impact strength, and the like. The modified paint can stabilize the dispersibility, ensure that the modified paint is uniformly distributed in the paint and avoid agglomeration and flocculation.

(2) The lignin partially replaces phenol to produce phenolic resin. And then epoxy modified phenolic resin is used. Preparing a coating main agent, and reacting and curing the coating main agent and amine before construction. The structure utilizes biological energy sources, and the cost is reduced. The heat resistance of the phenolic aldehyde is matched with the adhesive force of the epoxy, and the brittleness of the bio-based phenolic aldehyde is compensated by the bi-component thermosetting reaction, so that the corrosion resistance is further improved.

(3) In order to adapt to more surface substrates, hyperbranched adhesion promoters are used. The hyperbranched polymer has a plurality of branch points, molecular chains are not easy to wind, the terminal functional groups are complete, and the adhesive force and the cohesive force between the coating and the base layer can be greatly improved as the polar material has a plurality of attraction points.

(4) The hollow glass beads are internally provided with rarefied gas, the heat conductivity coefficient is low, the surface is hard, and the coating is resistant to scratch and chemical corrosion, so that the coating has the functions of heat insulation and heat preservation, cold and heat shrinkage resistance, is not easy to crack and fall off, the viscosity of the coating is not remarkably increased, the solvent amount is reduced, and the VOC is reduced.

(5) The natural nacre layer of shell has unique structure. The aragonite layer is changed, and the crack deflection and the fiber extraction are bound to occur. And the layers are tightly combined. The organic matrix of the regulation and control aragonite layer changes along with the tension, and the spiral structure thereof is loosened for a while and recovered. The random distribution of mineral bridges also increases crack deflection and fiber pull-out resistance. Several aspects together strengthen the structural toughness.

Detailed Description

The present invention will be described in detail with reference to specific examples.

Example 1

The component A comprises 30 percent of modified phenolic resin, 0.5 percent of organic silicon defoamer, 0.1 percent of base material wetting agent, 0.5 percent of hyperbranched coupling agent, 25 percent of iron oxide red powder, 3 percent of zinc phosphate, 5 percent of shell pearl layer, 2 percent of modified graphene oxide solution, 3 percent of glass hollow microspheres, 0.5 percent of flatting agent and 30.4 percent of butanol.

The component B comprises 100 parts of isophorone diamine and 10 parts of butanol.

The preparation method comprises the following steps:

preparation of modified graphene oxide solution

(1) 3g of graphite is put into 180ml of concentrated H with the mass ratio of 9:1₂SO₄And concentrated H₃PO₄The mixture is stirred fully, the temperature of the water bath is 4 ℃, and 9g of potassium permanganate is slowly added into the mixture. The reaction was carried out for half an hour at a bath temperature of 35 ℃. Adding 60 ℃ water into the solution, slowly adding enough hydrogen peroxide (until the solution color is bright yellow, no bubbles are generated) with the mass percent of 5%, reacting at the temperature of 80 ℃ for half an hour, centrifuging and washing the solution, and finally, setting the pH value of a filter cake to be 7. And (4) carrying out ultrasonic treatment and drying for later use.

(2) Ultrasonically dispersing graphene oxide into 0.5mg/ml aqueous solution, adding 1g of coupling agent KH570 into 200ml of aqueous solution, heating in a water bath at 70 ℃ for reacting for 24 hours, grafting coupling agent molecules to obtain modified graphene oxide solution, and drying for later use.

Preparation of (II) modified phenolic resin

(1)200 parts of lignin are added with 100 parts of phenol and 150 parts of sodium hydroxide at 60 ℃ and stirred for half an hour to obtain a mixed solution.

(2) 130 parts of 37% formaldehyde solution was added to the mixture to react at 70 ℃ for 2 hours. The reaction was continued for 1 hour while the temperature was raised to 90 ℃.

(3) And adjusting the pH of the reacted product to 7-8 to obtain bio-based phenolic resin, and reacting excessive ethyl peroxide with the phenolic resin at 120 ℃ for 1 hour to obtain the modified phenolic resin.

Preparation of (III) heavy duty anticorrosive paint

(1) Adding the modified phenolic resin into a batching kettle, adding 0.3% of defoaming agent, coupling agent and wetting agent, and uniformly stirring. Adding the modified graphene oxide solution, the iron oxide red powder, the zinc phosphate and the shell pearl layer while stirring. The slurry was ground to a fineness of 40 microns on a sand mill.

(2) And slowly stirring the ground slurry, adding a leveling agent, 0.2% of a defoaming agent and a diluent, and coating 4 cups of the slurry with the viscosity of 40-80 seconds. Then slowly adding the glass hollow micro-beads at a low speed. Obtaining the component A.

(4) And (3) uniformly mixing the components A and B at a ratio of 5:1, curing, coating, testing mechanical properties after two days under the standard condition, and testing resistance after seven days under the standard condition, wherein the specific results are shown in table 1.

Example 2

The component A comprises 40 percent of modified phenolic resin, 0.5 percent of organic silicon defoamer, 0.2 percent of base material wetting agent, 0.5 percent of hyperbranched coupling agent, 30 percent of iron oxide red powder, 8 percent of zinc phosphate, 10 percent of shell pearl layer, 5 percent of modified graphene oxide solution, 5 percent of glass hollow microspheres, 0.5 percent of flatting agent and 0.3 percent of butanol.

The component B comprises 100 parts of isophorone diamine and 10 parts of isophorone diamine.

The preparation method is the same as example 1.

Example 3

The component A comprises 45% of modified phenolic resin, 0.7% of organic silicon defoamer, 0.3% of base material wetting agent, 0.8% of hyperbranched coupling agent, 22% of iron oxide red powder, 5% of zinc phosphate, 6% of shell pearl layer, 4% of modified graphene oxide solution, 3% of glass hollow microspheres, 1.0% of flatting agent and 12.2% of butanol.

The preparation method is the same as example 1.

Example 4

The component A comprises 40% of modified phenolic resin, 0.7% of defoaming agent, 0.3% of base material wetting agent, 1.0% of hyperbranched coupling agent, 30% of iron oxide red powder, 6% of zinc phosphate, 5% of shell pearl layer, 4% of modified graphene oxide solution, 4% of glass hollow microspheres, 1.0% of flatting agent and 8% of butanol.

The preparation method is the same as example 1.

Example 5

The component A comprises 35 percent of modified phenolic resin, 0.6 percent of defoaming agent, 0.3 percent of base material wetting agent, 1.0 percent of hyperbranched coupling agent, 35 percent of iron oxide red powder, 5 percent of zinc phosphate, 4 percent of shell pearl layer, 4 percent of modified graphene oxide solution, 3 percent of glass hollow microspheres, 1.0 percent of flatting agent and 11.1 percent of butanol.

The preparation method is the same as example 1.

Comparative example 1

The component A comprises 30 percent of modified phenolic resin, 0.5 percent of defoaming agent, 0.1 percent of base material wetting agent, 0.5 percent of hyperbranched coupling agent, 25 percent of iron oxide red powder, 3 percent of zinc phosphate, 5 percent of shell pearl layer, 2 percent of graphene oxide solution, 3 percent of glass hollow microspheres, 0.5 percent of flatting agent and 30.4 percent of butanol.

The preparation method comprises the following steps:

preparation of graphene oxide solution

Step (1) was the same as in example 1.

(2) Ethanol is added before use, and graphene oxide is ultrasonically dispersed into a 2mg/ml solution.

(II) preparation of modified phenol resin the same as example 1.

(III) preparation of heavy duty anticorrosive paint same as example 1.

Comparative example 2

The component A comprises 30% of phenolic resin, 0.5% of defoaming agent, 0.1% of base material wetting agent, 0.5% of hyperbranched coupling agent, 25% of iron oxide red powder, 3% of zinc phosphate, 5% of shell pearl layer, 2% of modified graphene oxide solution, 3% of glass hollow microspheres, 0.5% of flatting agent and 30.4% of butanol.

The preparation method comprises the following steps:

(first) preparation of modified graphene oxide solution the same as in example 1.

Preparation of (di) phenolic resin

(2) The mixture was added to 130 parts of 37% formaldehyde solution and reacted at 70 ℃ for 2 hours. The reaction was continued for 1 hour while the temperature was raised to 90 ℃.

(3) And adjusting the pH of the reacted product to 7-8 to obtain the bio-based phenolic resin.

(III) preparation of heavy duty anticorrosive paint same as example 1.

Comparative example 3

The component A comprises 30 percent of commercial phenolic resin, 0.5 percent of defoaming agent, 0.1 percent of base material wetting agent, 0.5 percent of hyperbranched coupling agent, 25 percent of iron oxide red powder, 3 percent of zinc phosphate, 5 percent of shell pearl layer, 2 percent of modified graphene oxide solution, 3 percent of glass hollow micro-beads, 0.5 percent of flatting agent and 30.4 percent of butanol.

The preparation method comprises the following steps:

(II) preparation of heavy duty anticorrosive paint same as example 1.

Comparative example 4

The component A comprises 30 percent of modified phenolic resin, 0.5 percent of defoaming agent, 0.1 percent of base material wetting agent, KH5700.5 percent of coupling agent, 25 percent of iron oxide red powder, 3 percent of zinc phosphate, 5 percent of shell pearl layer, 0.2 percent of modified graphene oxide solution, 3 percent of glass hollow micro-beads, 0.5 percent of flatting agent and 30.4 percent of butanol.

The preparation method is the same as example 1.

The properties of the examples of the invention and the comparative examples are shown in Table 1.

TABLE 1

Specific test methods for heat resistance: and (3) placing the sample plate in an oven for 48 hours after drying for seven days, and judging whether the layout and a contrast plate without the oven have obvious changes such as cracking, peeling, discoloration and the like by naked eyes at the temperature of 200 ℃.

Claims

1. The high-toughness low-energy-consumption graphene biological basic weight anticorrosive coating is characterized by consisting of a component A and a component B, and the weight percentages of the components are as follows: the component A comprises 30-45% of modified phenolic resin, 0.5-0.8% of defoaming agent, 0.1-0.3% of base material wetting agent, 0.5-1.0% of hyperbranched coupling agent, 22-35% of iron oxide red powder, 2.5-8% of zinc phosphate, 5-10% of shell pearl layer, 2-5% of modified graphene oxide solution, 2-5% of hollow glass microsphere, 0.2-1.0% of flatting agent and the balance of diluent.

2. The high toughness low energy consumption graphene biobased heavy duty anticorrosive coating of claim 1, wherein the hyperbranched coupling agent is a hyperbranched polyurethane modified silane polymer; the diluent is butanol.

3. The method for preparing the high-toughness low-energy-consumption graphene biobased-weight anticorrosive coating according to claim 1, wherein the preparation method comprises the following steps:

firstly, preparing a modified graphene oxide solution;

secondly, preparing modified phenolic resin;

thirdly, preparing heavy anti-corrosion paint

(1) Respectively preparing a component A and a component B;

(2) and mixing the component A and the component B according to the mass ratio of 5:1 to prepare the heavy anti-corrosion coating.

4. The method for preparing the high-toughness low-energy-consumption graphene biobased-weight anticorrosive coating according to claim 3, wherein the modified graphene oxide solution is prepared by the following steps:

(1) putting graphite into concentrated H with the mass ratio of 9:1₂SO₄And concentrated H₃PO₄Fully stirring in mixed acid, putting potassium permanganate into the mixed acid at the water bath temperature of 4 ℃; reacting for half an hour at the water bath temperature of 35 ℃, and adding water at the temperature of 60 ℃ into the reaction solution; adding enough 5 mass percent hydrogen peroxide, reacting at 80 ℃ for half an hour, then centrifugally washing the solution, and drying by ultrasonic treatment for later use;

(2) ultrasonically dispersing graphene oxide into an aqueous solution, adding a coupling agent into the aqueous solution, heating in a water bath for reaction, grafting molecules of the coupling agent to obtain a modified graphene oxide solution, and then treating and drying for later use;

5. The method for preparing the high-toughness low-energy-consumption graphene biobased weight anticorrosive coating according to claim 4, wherein the coupling agent in the step (2) is KH570, and the reaction is carried out at 70 ℃ for 24 hours.

6. The preparation method of the high-toughness low-energy-consumption graphene biobased heavy-duty anticorrosive coating according to claim 3, wherein the preparation method of the modified phenolic resin comprises the following steps: adding 80-200 parts of lignin into 100 parts of phenol and 150 parts of sodium hydroxide at 60 ℃, stirring for half an hour, adding 130 parts of 37% formaldehyde solution, reacting at 70 ℃ for 2 hours, heating to 90 ℃ and reacting for 1 hour, and adjusting the pH of the reacted product to obtain the bio-based phenolic resin; and adding excessive ethylene oxide, and reacting at 120 ℃ for 1h to obtain the modified phenolic resin.

7. The preparation method of the high-toughness low-energy-consumption graphene biobased-weight anticorrosive coating according to claim 3, wherein the preparation method of the component A comprises the following steps:

(1) adding the modified phenolic resin into a material mixing kettle, adding a defoaming agent, a hyperbranched coupling agent and a wetting agent, uniformly stirring, adding a modified graphene oxide solution, iron oxide red powder, zinc phosphate and a shell pearl layer under stirring, and grinding the slurry to the fineness of 40 microns by a sand mill;

(2) and slowly stirring the ground slurry, adding a leveling agent, a defoaming agent and a diluting agent, coating for 4 cups, keeping the viscosity at 40-80 seconds, and slowly adding the glass hollow microspheres at a low speed to obtain the component A.

8. The preparation method of the high-toughness low-energy-consumption graphene biobased-weight anticorrosive coating according to claim 3, wherein the preparation method of the component B comprises the following steps: adding a diluent into alicyclic amine, and stirring to obtain a component B, wherein the alicyclic amine is isophorone diamine.