CN113897118A - Environment-friendly ultrahigh-solid-content epoxy coating orange paint and preparation method and application thereof - Google Patents

Abstract

The invention relates to an environment-friendly type epoxy coating with ultrahigh solid content, namely orange paint, and a preparation method and application thereof, wherein d-limonene is used for replacing a traditional chemical solvent to reduce the viscosity of a solvent-free epoxy coating, so that the solvent-free epoxy coating with ultrahigh solid content is formed, the solid content of the solvent-free epoxy coating is more than 95 percent, the solvent-free epoxy coating can be directly used without adding a diluent, the excellent corrosion resistance is kept, harmful gas volatilization is avoided, the environment-friendly type epoxy coating with ultrahigh solid content is beneficial to the health of construction personnel, and the environment-friendly type epoxy coating with ultrahigh solid content does not pollute air and soil and water.

Description

Environment-friendly ultrahigh-solid-content epoxy coating orange paint and preparation method and application thereof

Technical Field

The invention belongs to the field of chemical coatings, and particularly relates to an environment-friendly ultrahigh-solid-content epoxy coating orange peel paint as well as a preparation method and application thereof.

Background

The solvent is an important component of the coating, the main function of the solvent is to reduce the viscosity of the coating, the construction is convenient, and the solvent is volatilized into the atmosphere after the coating is formed into a film, so that the traditional solvent coating seriously pollutes the atmospheric environment by the volatilized chemical solvent and is limited in use. The paint is a product favored by the market in the fields of heavy-duty anticorrosive paint, such as high-solid paint, solvent-free paint and water-based industrial paint. However, the three products are not really environment-friendly, a large amount of organic solvent is volatilized from the high-solid-content paint, a large amount of diluent is required to cause air pollution during the construction of the solvent-free paint, and the water-based paint which is generally considered to be environment-friendly is difficult to treat the pollution of soil and water because the resin is dissolved in water, and cannot meet the requirement on the performance of the heavy-duty anticorrosion field. The high-performance environment-friendly coating which does not pollute air, water and soil, does not harm constructors and has excellent corrosion resistance is needed.

Disclosure of Invention

In light of the above shortcomings of the prior art, the present invention aims to provide an ultra-high solid content epoxy coating using d-limonene as a plant-based environment-friendly solvent, and a preparation method and applications thereof. The environment-friendly epoxy coating with ultrahigh solid content at least has the following advantages: the paint has the advantages of no volatilization of harmful gases, health benefits to constructors, low viscosity, no need of adding any diluent during use, high thickness, high strength, good toughness, excellent adhesion, long-acting water penetration resistance and chemical corrosion resistance; the environment-friendly ultrahigh solid content epoxy coating does not pollute air and soil and water. The paint film color of the paint is adjusted to orange color and orange fragrance, and the environment-friendly epoxy paint with ultrahigh solid content is called orange paint.

In order to solve the environmental protection problem of the existing anticorrosive paint, the invention uses d-limonene to replace the traditional chemical solvent to reduce the viscosity of the solvent-free epoxy paint, so that the solvent-free epoxy paint becomes the environment-friendly epoxy paint with the solid content of more than 95 percent, and the solvent-free epoxy paint can be directly used without adding a diluent, thereby maintaining excellent anticorrosive performance. The d-limonene is a natural component existing in various fruits (mainly citrus), vegetables and spices, can be directly extracted from plants, has wide application, has good cough relieving, phlegm eliminating and bacteriostatic effects, can be used in the spice industry, and can also be used as an additive in the food industry. The orange fragrance is beneficial to the health of constructors when used in the coating, and the orange fragrance is pleasant.

In order to realize the purposes, the adopted technical scheme is as follows:

the invention provides a two-component environment-friendly type epoxy coating orange paint with ultrahigh solid content. The environment-friendly epoxy coating with ultrahigh solid content comprises a main paint component and a curing agent component, wherein:

the main paint component comprises: 30-45 parts of low-viscosity bisphenol A epoxy resin, 4-7 parts of petroleum resin, 5-9 parts of modified reactive diluent, 4-10 parts of d-limonene, 0.5-1.5 parts of hyper-dispersant, 0.5-1.5 parts of anti-settling and anti-sagging agent, 40-50 parts of low-oil-absorption pigment and filler, 0.5-1.5 parts of silane coupling agent and 0.1-0.5 part of defoaming agent

The curing agent component comprises: 50-70 parts of modified fatty amine and 30-40 parts of phenolic aldehyde amine.

By adopting the embodiment of the invention, the environment-friendly epoxy coating with ultrahigh solid content can be effectively prepared, and in the product, the flexibility and the adhesive force of the formed paint film can be improved by blending the bisphenol A epoxy resin and the petroleum resin; the inventors have found that when D-limonene is used alone without a reactive diluent in the main paint component, the viscosity reducing effect is not good because it is not well compatible with epoxy resin. When a proper active diluent is added, the viscosity of the D-limonene is reduced in a synergistic way with the D-limonene, so that a good cosolvent effect is achieved, the viscosity of a system can be remarkably reduced by the active diluent, the compactness of a formed paint film can be improved, and the viscosity of the D-limonene can be greatly and directly reduced to 80KU for construction and use; the low oil absorption pigment and filler obviously reduces the adsorption of powder to resin, reduces the viscosity of the coating, and can also improve the impact resistance and the medium permeation resistance of the formed paint film; the pigment combination can form an orange paint film with the color similar to that of orange, and the orange paint film smells the orange fragrance and is happy. The hyper-dispersant can better wrap the resin and the pigment, so that the viscosity of the coating is effectively reduced; the silane coupling agent can coat and modify the surface of the powder raw material, so that the powder raw material and the resin can be better wrapped, and meanwhile, a chemical reaction can be generated on the surface of steel, so that the adhesive force of a paint film is increased; the viscosity of the modified fatty amine is low, so that the curing time of a paint film can be adjusted, and the moisture resistance and stability of the paint film can be enhanced; the phenolic aldehyde amine can obviously improve the wetting performance of the coating on a wet surface and improve the adhesive force of a paint film.

Furthermore, the raw materials are used in a matching way and the proportion of the raw materials is further controlled, so that the viscosity of the prepared coating can be further reduced, the viscosity of the coating is not more than 80KU, and the flexibility, the impact resistance, the adhesive force and the comprehensive corrosion resistance of the formed paint film can be further improved. Therefore, the environment-friendly ultrahigh solid content epoxy coating has at least the following advantages: the resin has ultrahigh solid content, is nontoxic, has no harmful gas volatilization, has no pollution to the atmosphere, is insoluble in water, has no pollution to water and soil, and is beneficial to the health of constructors; the paint can be mixed and used in a normal temperature environment, the viscosity of the mixed paint is ultralow, no diluent is required to be added, and the paint can be directly sprayed by using a conventional spray gun; the construction can be carried out on a wet surface; the paint is convenient to use, good in atomization and quick to dry after being sprayed, and the formed paint film is compact, high in strength, good in toughness, excellent in adhesive force, excellent in long-acting water penetration resistance and chemical corrosion resistance; the cathodic disbonding resistance is good.

In addition, the ultra-high solid content epoxy coating according to the above embodiment of the present invention may also have the following additional technical features:

in some embodiments of the present invention, in the main paint component, the viscosity of the low-viscosity bisphenol a epoxy resin is not more than 10000mPa · s/25 ℃, for example, not more than 9000mPa · s/25 ℃, not more than 7000mPa · s/25 ℃, not more than 5000mPa · s/25 ℃, or not more than 3000mPa · s/25 ℃, and the like, and by further controlling the viscosity of the low-viscosity bisphenol a epoxy resin in the present invention, the viscosity of the finally formulated coating can be further reduced, thereby further facilitating direct spray coating construction using a conventional spray gun. .

In some embodiments of the invention, the d-limonene is 1-methyl-4- (1-methylvinyl) cyclohexene having the formula C₁₀H₁₆. The orange-flavored orange-peel coating is colorless liquid with orange fragrance, is easy to dissolve in an organic solvent, can assist an active diluent, and greatly reduces the viscosity of the coating. The D-limonene selected in the present invention is not particularly limited, and may be selected by those skilled in the art according to actual needs. For example, Jiangxi Jiajinlinhua product NMX-02, Brazil LDC \ FMI, etc.

The viscosity of the system can be obviously reduced by properly increasing the content of D-limonene in the main paint component, but when the content of D-limonene is 0-5%, the mixed viscosity of the paint is greatly reduced from 130KU to 75KU, the paint can be well sprayed and used by an airless spray gun, and the effect required by heavy-duty construction is achieved. When the D-limonene content continues to increase, the viscosity does not change much.

In some embodiments of the invention, the reactive diluent is at least one selected from neodecanoic acid glycidyl ester, carbon twelve to carbon tetradecyl glycidyl ether and butyl glycidyl ether, so that not only can the viscosity of the system be reduced, but also the compactness of the paint film can be further increased, and the comprehensive performance of the paint film can be remarkably improved;

when the reactive diluent is neodecanoic acid glycidyl ester, the d-limonene has the best viscosity reduction effect with the reactive diluent. The viscosity reduction effect is poor when the butyl glycidyl ether is used in cooperation with the butyl glycidyl ether. 5% neodecanoic acid glycidyl ester and 5% D-limonene, wherein the mixing viscosity is 75 KU; 5% butyl glycidyl ether and 5% D-limonene, and 90KU at mixed viscosity.

In some embodiments of the present invention, the anti-settling and anti-sagging agent is at least one selected from the group consisting of polyamide wax and polyethylene wax.

In some embodiments of the present invention, the low oil absorption pigment and filler is at least one selected from the group consisting of molybdenum zinc phosphate, barite, ferrotitanium powder, cloud iron powder and aluminum powder, so that the stability of the first main paint component and the prepared paint can be significantly improved, and the impact resistance and the medium permeation resistance of the paint film can be significantly increased;

the low-viscosity bisphenol a epoxy resin and the petroleum resin used in the present invention are not particularly limited, and those skilled in the art can select them according to actual needs. For example, the low viscosity bisphenol a epoxy resin may be at least one selected from the group consisting of bisphenol a type liquid reducing resin having shell brand EPIKOTE827, nanasian NPEL 127 bisphenol a epoxy resin, and meta-bonding YPE-127 bisphenol a liquid epoxy resin; the petroleum resin may be at least one selected from the group consisting of Lutecger C30, Lutecger LA700, and Cologne PL 1000.

The accelerator used in the present invention is not particularly limited, and can be selected by those skilled in the art according to the actual needs. For example, the accelerator may be at least one selected from modified amines DMP30 and K54, whereby the drying speed of the paint film can be increased and workability can be improved.

The hyperdispersant can be at least one selected from the group consisting of hyperdispersant Lubrium 20000, BYK-2000 and Kaster 4200, so that the resin and the pigment can be better wrapped, and the viscosity of the coating can be effectively reduced; the silane coupling agent can be at least one selected from KH550 and Dow Corning Z-6040, so that the powdery raw material can be subjected to surface modification, the compatibility of the powdery raw material and a resin raw material is improved, a chemical reaction can be generated on the surface of steel, and the adhesive force of a paint film is increased.

In some embodiments of the present invention, the fineness of the main paint component is not greater than 80 microns, for example, may be not greater than 75 microns, not greater than 70 microns, not greater than 65 microns, and the like, whereby the flatness, smoothness, color, durability, and the like of the formed paint film can be further improved.

According to a second aspect of the present invention, there is provided a process for preparing the above ultra-high solid content epoxy coating. According to an embodiment of the invention, the main paint component is prepared according to the following steps:

(1) adding low-viscosity bisphenol A epoxy resin, petroleum resin, reactive diluent, d-limonene, hyperdispersant, silane coupling agent and low-oil-absorption pigment filler into a container according to a predetermined proportion, uniformly stirring at a high speed, and then continuously stirring at a low speed for more than 4 hours;

(2) adding an anti-settling anti-sagging agent with a predetermined proportion into the mixed solution obtained in the step (1) and dispersing at a high speed for 20-30 minutes;

(3) adding a defoaming agent in a preset proportion into the mixed solution obtained in the step (2) and uniformly dispersing;

(4) sequentially grinding, dispersing and filtering the mixed solution obtained in the step (3) to obtain a main paint component,

the curing agent component is prepared according to the following steps: uniformly mixing the modified fatty amine and the phenolic aldehyde amine according to a predetermined proportion, and filtering to obtain the curing agent component.

According to the method for preparing the ultrahigh-solid-content epoxy coating, the raw materials are matched and used, and the raw material proportion and the preparation conditions are further controlled, so that the viscosity of the prepared coating can be further reduced, and the flexibility, the impact resistance, the adhesive force and the comprehensive corrosion resistance of a formed paint film can be further improved. For example, in the step (1), the resin and the pigment can be more fully soaked by controlling the low-speed stirring time to be not less than 4 hours, the coating is more perfect, the viscosity can be fully reduced, and the compactness of a paint film can be improved. The main paint component is prepared at the temperature of 60-75 ℃, and the inventor finds that when the main paint component is prepared, the temperature is kept between 60-75 ℃, such as 60 ℃, 65 ℃ or 70 ℃, so that the main paint component has a very critical effect on improving the performance of the paint: firstly, the molecular chain of the low-viscosity bisphenol A epoxy resin petroleum resin can be fully opened and unfolded without winding, so that the viscosity of the coating is reduced; secondly, the pigment and the filler can be fully soaked with the silane coupling agent and the epoxy resin, so that the optimal coating state of the pigment and the resin is achieved; third, the activity of an anti-settling anti-sagging agent such as polyamide wax powder can be activated, thereby improving the anti-sagging property and storage stability of the pigment. Therefore, the viscosity of the coating prepared from the ultrahigh-solid-content epoxy coating can be further reduced and the comprehensive performance of a paint film formed by the coating can be remarkably improved by controlling the temperature condition.

According to the third aspect of the invention, the invention provides the application of the environment-friendly ultrahigh solid content epoxy coating, the solid content of the environment-friendly ultrahigh solid content epoxy coating is ultrahigh, the thickness of a single-pass formed film can reach more than 300 micrometers, the paint film is compact, the anticorrosion capability is strong, and the environment-friendly ultrahigh solid content epoxy coating can be used for industrial anticorrosion including ocean engineering, ships, ports and docks, electric power, petrifaction, mines, steel structures and bridges. Therefore, the corrosion of the metal base material can be effectively inhibited, and the service life of the metal base material is obviously prolonged. The method realizes real environmental protection in the field of industrial heavy-duty anticorrosive coatings.

Compared with the prior art, the invention has the beneficial effects that:

(1) ecological and environment-friendly, nontoxic and free of harmful gas volatilization; (2) the method is harmless to the health of workers and beneficial; (3) the ultra-low viscosity is not more than 80KU, and the coating can be directly sprayed by a conventional spray gun; (4) has excellent adhesion (not less than 10 MPa); (5) the paint film has good flexibility and impact resistance; (6) excellent water vapor permeation resistance and chemical corrosion resistance: (7) good cathodic disbonding resistance: matched with cathodic protection, has very good cathodic protection characteristics.

Detailed Description

The present invention is described below with reference to examples, which are provided for illustration only and are not intended to limit the scope of the present invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.

The environment-friendly ultrahigh solid content epoxy coating comprises the following raw material sources:

wherein, the raw material sources of the main paint component are as follows:

low viscosity bisphenol a epoxy resin: shell EPIKOTE827 epoxy resin

Petroleum resin: hydrocarbon petroleum resin Lvteger C30

Active diluent: neodecanoic acid glycidyl ester (Hebei Si you)

d-limonene: jiangxi Jiajinlinhua NMX-02

Hyper-dispersant: ultra-dispersant Lu Bo run 20000

Anti-sinking anti-sagging agent: polyamide wax anti-sinking anti-sagging agent 6650 (Nanbenghua)

Low oil absorption pigment and filler: molybdenum zinc phosphate, barite, schlempe powder, aluminum powder and iron titanium powder

Silane coupling agent: KH550

And (3) defoaming agent: organosilicon defoaming agent TEGAO900

The raw material sources of the curing agent component are as follows:

modified fatty amine: chemical engineering of mai-chu-ji diagram

Phenolic aldehyde amine: cadeland rice

Example 1

1) Environment-friendly type epoxy coating with ultrahigh solid content

The environment-friendly ultrahigh-solid-content epoxy coating comprises a main coating component and a curing agent component, wherein the main coating component comprises:

40 parts by weight of a low-viscosity bisphenol A epoxy resin (EPIKOTE827),

5 parts by weight of hydrocarbon petroleum resin (Lutege C30),

5 parts by weight of glycidyl neodecanoate,

5 parts by weight of d-limonene,

1 part by weight of hyperdispersant lubrian 20000,

1.5 parts by weight of polyamide wax anti-settling anti-sagging agent 6650,

10.8 parts by weight of poly-phosphorus-molybdenum-zinc,

10 parts by weight of barite,

16 parts by weight of ferrotitanium powder,

5 parts by weight of aluminum powder,

0.5 part by weight of a silane coupling agent KH550,

0.2 part by weight of a silicone defoamer TEGAO 900;

the curing agent component comprises:

10 parts by weight of modified aliphatic amine,

10 parts by weight of a phenolic amine.

2) Method for preparing epoxy coating with ultrahigh solid content

The raw materials were prepared according to the components and amounts described above.

Preparation of the main paint component: sequentially adding low-viscosity bisphenol A epoxy resin, petroleum resin, an active diluent, d-limonene, a hyperdispersant, a silane coupling agent and a low-oil-absorption pigment filler into a dispersion kettle according to the above proportion, uniformly stirring at a high speed, continuously stirring at a low speed for more than 4 hours, then adding an anti-settling anti-sagging agent, dispersing at a high speed, keeping the temperature at 60-75 ℃, adding an antifoaming agent after continuously stirring for 20-30 minutes, uniformly dispersing, controlling the fineness to be below 80 micrometers, filtering and filling after the detection is qualified.

Preparation of the curing agent component: adding modified fatty amine and phenol aldehyde amine, mixing, filtering and filling.

Example 2

The difference from example 1 is that:

the environment-friendly ultrahigh-solid-content epoxy coating comprises a main paint component and a curing agent component, wherein:

the main paint component comprises

38 parts by weight of a low-viscosity bisphenol A epoxy resin (EPIKOTE827),

6 parts by weight of hydrocarbon petroleum resin (Lutege C30),

6 parts by weight of glycidyl neodecanoate,

4 parts by weight of d-limonene,

1 part by weight of hyperdispersant lubrian 20000,

1.5 parts by weight of polyamide wax anti-settling anti-sagging agent 6650,

10.8 parts by weight of poly-phosphorus-molybdenum-zinc,

11 parts by weight of barite,

16 parts by weight of ferrotitanium powder,

5 parts by weight of aluminum powder,

0.5 part by weight of a silane coupling agent KH550,

0.2 part by weight of a silicone defoamer TEGAO 900;

the curing agent component comprises:

10 parts by weight of modified aliphatic amine,

10 parts by weight of a phenolic amine.

Example 3

The difference from example 1 is that:

the environment-friendly ultrahigh-solid-content epoxy coating comprises a main paint component and a curing agent component, wherein: the main paint component comprises

45 parts by weight of low-viscosity bisphenol A epoxy resin (EPIKOTE827),

5 parts by weight of hydrocarbon petroleum resin (Lutege C30),

5 parts by weight of glycidyl neodecanoate,

5 parts by weight of d-limonene,

1 part by weight of hyperdispersant lubrian 20000,

1.5 parts by weight of polyamide wax anti-settling anti-sagging agent 6650,

10.8 parts by weight of poly-phosphorus-molybdenum-zinc,

9 parts by weight of barite,

12 parts by weight of ferrotitanium powder,

5 parts by weight of aluminum powder,

0.5 part by weight of a silane coupling agent KH550,

0.2 part by weight of a silicone defoamer TEGAO 900;

the curing agent component comprises:

10 parts by weight of modified aliphatic amine,

10 parts by weight of a phenolic amine.

Testing

The color and appearance, non-volatiles, sprayability, viscosity, fineness, drying time, adhesion, flexibility, impact strength, stability, cathodic disbondment resistance and corrosion resistance of the ultra-high solid epoxy coatings "orange peel" prepared in examples 1-3 were evaluated, and the technical indices and evaluation results are shown in table 1.

TABLE 1 evaluation results of the properties of the environmentally friendly ultra-high solid content epoxy coating obtained in examples 1 to 3

As can be seen from the data in Table 1, the environment-friendly type epoxy coating with ultrahigh solid content prepared by the invention has ultralow viscosity of not more than 80KU, and can be directly sprayed by a conventional spray gun; the storage stability of the main paint component and the curing agent component is not less than 1 year, the solid content is more than 94 percent, the surface drying time is not more than 4 hours, the actual drying time is not more than 24 hours, the adhesion with a matrix is not less than 10 MPa, the flexibility is not more than 2mm, the impact strength is not less than 50cm, the cathodic disbonding resistance (1500 hours) is less than 8mm, and the salt spray resistance (3000 hours) and the artificial seawater resistance (3000 hours) are free from foaming corrosion.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, but rather as the subject matter of the invention is to be construed in all aspects and as broadly as possible, and all changes, equivalents and modifications that fall within the true spirit and scope of the invention are therefore intended to be embraced therein.

Claims (9)

1. An environment-friendly type ultrahigh-solid-content epoxy coating orange paint is characterized by comprising a main paint component and a curing agent component, wherein,

the main paint component comprises: 30-45 parts of low-viscosity bisphenol A epoxy resin, 4-7 parts of petroleum resin, 5-9 parts of modified reactive diluent, 4-10 parts of d-limonene, 0.5-1.5 parts of hyper-dispersant, 0.5-1.5 parts of anti-settling and anti-sagging agent, 40-50 parts of low-oil-absorption pigment and filler, 0.5-1.5 parts of silane coupling agent and 0.1-0.5 part of defoaming agent;

the curing agent component comprises: 8-14 parts of modified fatty amine and 6-12 parts of phenolic aldehyde amine.

2. The environment-friendly type ultra-high solid content epoxy paint orange peel paint as claimed in claim 1, wherein the low viscosity bisphenol A epoxy resin has a viscosity of not more than 10000 mPa-s/25 ℃.

3. The environment-friendly type ultra-high solid content epoxy coating orange peel paint as claimed in claim 1, wherein the d-limonene is 1-methyl-4- (1-methylvinyl) cyclohexene, and the molecular formula is C₁₀H₁₆。

4. The environment-friendly type ultra-high solid content epoxy coating orange peel paint as claimed in claim 1, wherein the reactive diluent is at least one of neodecanoic acid glycidyl ester, carbon-dodecyl-to-carbon-tetradecyl glycidyl ether and butyl glycidyl ether.

5. The environment-friendly type ultra-high solid content epoxy coating orange paint as claimed in claim 1, wherein the anti-settling and anti-sagging agent is at least one selected from polyamide wax and polyethylene wax.

6. The orange peel paint as recited in claim 1, wherein the low oil absorption pigment and filler is at least one selected from the group consisting of molybdenum zinc phosphate, barite, ferrotitanium powder, cloud iron powder and aluminum powder.

7. The environment-friendly type ultra-high solid content epoxy coating orange peel paint as claimed in claim 1, wherein the fineness of the main paint component is not more than 80 μm.

8. A preparation method of the environment-friendly type ultra-high solid content epoxy coating orange peel paint as claimed in any one of claims 1 to 7,

the main paint component is prepared according to the following steps:

(1) adding low-viscosity bisphenol A epoxy resin, petroleum resin, reactive diluent, D-limonene, hyperdispersant, silane coupling agent and low-oil-absorption pigment filler into a container according to a predetermined proportion, uniformly stirring at a high speed, and then continuously stirring at a low speed for more than 4 hours;

(2) adding an anti-settling anti-sagging agent with a predetermined proportion into the mixed solution obtained in the step (1) and dispersing at a high speed for 20-30 minutes;

(3) adding a defoaming agent in a preset proportion into the mixed solution obtained in the step (2) and uniformly dispersing;

(4) sequentially grinding, dispersing and filtering the mixed solution obtained in the step (3) to obtain a main paint component;

the curing agent component is prepared according to the following steps: uniformly mixing the modified fatty amine and the phenolic aldehyde amine according to a predetermined ratio, and filtering to obtain a curing agent component;

and finally, uniformly stirring the main paint, adding the curing agent, and uniformly mixing and stirring at a low speed to obtain the paint.

9. An application of the environment-friendly type ultra-high solid content epoxy coating orange peel paint as claimed in any one of claims 1 to 7 in the field of industrial heavy-duty anticorrosive coatings.