CN109385185B - Water-based hemicellulose/cellulose/acrylic acid-epoxy resin coating and preparation method thereof - Google Patents
Water-based hemicellulose/cellulose/acrylic acid-epoxy resin coating and preparation method thereof Download PDFInfo
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- CN109385185B CN109385185B CN201810954889.5A CN201810954889A CN109385185B CN 109385185 B CN109385185 B CN 109385185B CN 201810954889 A CN201810954889 A CN 201810954889A CN 109385185 B CN109385185 B CN 109385185B
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- C—CHEMISTRY; METALLURGY
- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
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- C—CHEMISTRY; METALLURGY
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention discloses a water-based hemicellulose/cellulose/acrylic acid-epoxy resin coating and a preparation method thereof. The coating consists of acrylic acid modified epoxy resin coating and filler, wherein the filler accounts for 0.5 to 5 percent of the mass fraction of the acrylic acid modified epoxy resin; wherein, the acrylic acid in the acrylic acid modified epoxy resin accounts for 10 to 20 percent of the mass fraction of the epoxy resin; the filler is hemicellulose and cellulose. Firstly, modifying epoxy resin with acrylic acid to obtain an acrylic acid-epoxy resin coating; then, mixing filler hemicellulose and cellulose, ultrasonically dispersing the mixture in deionized water, and adding the mixture into an acrylic acid-epoxy resin coating to obtain a mixed coating; defoaming the mixed coating; obtaining the aqueous hemicellulose/cellulose/acrylic acid-epoxy resin coating. The raw materials related by the invention are widely and easily available, the environment is protected, no pollution is caused, and the cellulose and the hemicellulose are inexhaustible. And the coating has the advantages of high stability, excellent corrosion resistance and the like.
Description
Technical Field
The invention relates to the technical field of coatings, and particularly relates to a water-based hemicellulose/cellulose/acrylic acid-epoxy resin coating and a preparation method thereof.
Background
In China, environmental protection is a very concerned problem, and the water-based epoxy resin also becomes a focus of research due to the advantages of the water-based epoxy resin in the aspect of environmental protection. With the increasing environmental protection situation, in the paint industry, research on water-based anticorrosive paints with low organic volatile is an important trend in the development of anticorrosive paints. The preparation of high-performance water-based anticorrosive resin, which is the most important component of water-based anticorrosive paint, is one of the problems to be solved urgently. The epoxy resin is a thermosetting high polymer material with good adhesive property, adhesive force, electrical insulation property and chemical stability, is used as a resin matrix of paint, adhesive, composite material and the like, and has wide application fields. The epoxy resin is divided into solvent type epoxy resin and water-based epoxy resin, wherein the solvent used in the solvent type epoxy resin is an organic solvent, which is a volatile and toxic component, so the demand of the solvent type epoxy resin is increasingly reduced; however, the water-soluble epoxy resin uses water as a solvent, and is natural and pollution-free, so that the demand of the solvent-type epoxy resin is certainly exceeded by the water-soluble epoxy resin, and even complete replacement is quite possible. Therefore, more and more researchers are dedicated to develop environment-friendly water-based epoxy resin.
Cellulose and hemicellulose are abundant in nature and are commonly found in most plants. The hemicellulose has a polysaccharide ring structure, so that the hemicellulose is easy to form a compact macromolecular network structure, and the macromolecular network structure enables the hemicellulose to have good gas barrier performance, especially good oxygen barrier performance, and oxygen is one of the main factors causing corrosion. Therefore, the corrosion resistance of the hemicellulose coating is obviously improved. In addition, the content of cellulose in plants is higher than that of hemicellulose, and the cellulose has excellent performances of high hardness, high strength, high crystallinity, high surface tension, high reactivity and the like and special properties of nanoparticles. Because of these properties, the barrier, thermal and mechanical properties of the polymer can be improved when it is incorporated into a coating. Therefore, the prospect of adding the mixture of the hemicellulose and the cellulose into the acrylic acid-epoxy resin coating is quite bright.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a novel safe, environment-friendly and pollution-free water-based hemicellulose/cellulose/acrylic acid-epoxy resin coating, and the invention also aims to provide a preparation method of the coating, which is mainly used for the anticorrosion of steel. The acrylic acid-epoxy resin coating has the characteristics of no toxicity, no odor, low cost, wide and easily available raw materials, renewability and the like, and the anticorrosive performance is further improved on the basis of the pure acrylic acid-epoxy resin coating.
The technical scheme of the invention is as follows:
an aqueous hemicellulose/cellulose/acrylic acid-epoxy resin coating is characterized in that: the coating consists of acrylic acid modified epoxy resin coating and filler, wherein the filler accounts for 0.5 to 5 percent of the mass fraction of the acrylic acid modified epoxy resin in the acrylic acid modified epoxy resin coating; wherein, the acrylic acid in the acrylic acid modified epoxy resin coating accounts for 10 to 20 percent of the mass fraction of the epoxy resin; the filler is hemicellulose and cellulose.
Preferably, the mass ratio of the hemicellulose to the cellulose is (0.5-3): 1.
preferably, the epoxy resin in the acrylic modified epoxy resin is epoxy resin E-12, epoxy resin E-20, epoxy resin E-44 or epoxy resin E-51. More preferably epoxy resin E-44.
Preferably, the acrylic acid is: alpha-methacrylic acid.
The invention also provides a preparation method of the aqueous hemicellulose/cellulose/acrylic acid-epoxy resin coating, which comprises the following specific steps:
(1) firstly, modifying epoxy resin with acrylic acid to obtain an acrylic acid-epoxy resin coating; then, mixing filler hemicellulose and cellulose, ultrasonically dispersing the mixture in deionized water, and adding the mixture into an acrylic acid-epoxy resin coating to obtain a mixed coating;
(2) defoaming the mixed coating; obtaining the aqueous hemicellulose/cellulose/acrylic acid-epoxy resin coating.
The above-mentioned epoxy resin coating modified with acrylic acid is modified by a conventional method. The method comprises the following specific steps: firstly), grafting hydrophilic acrylic acid monomer onto epoxy resin, wherein the mass fraction of acrylic acid accounts for 10-20% of that of the epoxy resin, secondly), fully dissolving ethylenediamine into deionized water to prepare alkali liquor, cooling the reaction product obtained in the first step to room temperature, slowly dripping the alkali liquor into the reaction product under the stirring state until the pH value of the product reaches about 9.0, and obtaining the acrylic acid-epoxy resin coating.
Preferably, the mass solid content of the coating after mixing in the step (1) is controlled to be 10-60%. Preferably, the mass ratio of the hemicellulose to the cellulose is (0.5-3): 1.
preferably, the ultrasonic dispersion parameters in step (1) are as follows: the time of ultrasonic dispersion is 10-30 min.
Preferably, the defoaming treatment method in the step (2) adopts one or two of standing, negative pressure and ultrasonic defoaming.
The performance test method of the prepared coating comprises the following steps:
firstly, generating a coating film on a steel plate by adopting a solvent evaporation method; preferably, the solvent evaporation time is 12-24 h. Then vacuum drying is carried out, the solvent remained in the coating film is further evaporated, and then the corrosion resistance test is carried out; the parameters of the preferred vacuum drying are: drying for 24-48 h at 40-60 ℃, then heating to 70-90 ℃, and continuing drying for 12-24 h.
Has the advantages that:
the invention discloses a water-based hemicellulose/cellulose/acrylic acid-epoxy resin coating, and a preparation method thereof. The raw materials related by the invention are widely and easily available, the environment is protected, no pollution is caused, and the cellulose and the hemicellulose are inexhaustible. And the coating has the advantages of high stability, excellent corrosion resistance and the like.
Detailed Description
The following examples are intended to illustrate the invention without limiting it.
The acrylic-epoxy coatings of the following examples were prepared by the following method: the method comprises the following specific steps: firstly), grafting hydrophilic acrylic acid monomer onto epoxy resin, wherein the mass fraction of acrylic acid accounts for 10-20% of that of the epoxy resin, secondly), fully dissolving ethylenediamine into deionized water to prepare alkali liquor, cooling the reaction product obtained in the first step to room temperature, slowly dripping the alkali liquor into the reaction product under the stirring state until the pH value of the product reaches about 9.0, and obtaining the acrylic acid-epoxy resin coating.
Example 1
In this embodiment, a water-based hemicellulose/cellulose/acrylic acid-epoxy resin coating specifically includes the following steps:
weighing 10 parts of acrylic acid modified epoxy resin coating, wherein the mass fraction of acrylic acid in the epoxy resin E-44 is 10%, and adding filler hemicellulose and cellulose according to the mass ratio of 2: 1. The filler accounts for 2 percent of the mass of the acrylic modified epoxy resin coating. The mixture of the hemicellulose and the cellulose is added into deionized water for ultrasonic dispersion for 10min, so that the hemicellulose and the cellulose are uniformly dispersed in the deionized water, and then the uniformly dispersed solution is slowly added into the acrylic acid modified epoxy resin coating. And (3) keeping the mass solid content of the mixed coating to be 30%, continuing to magnetically stir for 6h, then performing ultrasonic defoaming for 15min, and then standing and defoaming for 12h to obtain the water-based hemicellulose/cellulose/acrylic acid-epoxy resin coating.
Uniformly coating the coating on No. 45 carbon steel, evaporating the solvent at room temperature for 24h, then putting the coating into a vacuum drying oven, drying at 60 ℃ for 48h, then heating to 80 ℃ and continuing to dry for 24 h. And (5) after drying, performing corrosion resistance test. The salt spray resistance of the paint reaches 130h and the adhesive force is 2 grade by measurement.
Comparative example 1
Weighing 10 parts of acrylic acid modified epoxy resin coating, wherein the mass fraction of acrylic acid in the epoxy resin E-44 is 10%, slowly adding deionized water into the coating, controlling the mass solid content of the coating to be 30%, continuing to magnetically stir for 6h, then performing ultrasonic defoaming for 30min, and then standing for 12h to obtain the water-based hemicellulose/cellulose/acrylic acid-epoxy resin coating.
Uniformly coating the coating on No. 45 carbon steel, evaporating the solvent at room temperature for 24h, then putting the coating into a vacuum drying oven, drying at 40 ℃ for 48h, then heating to 70 ℃ and continuing to dry for 24 h. And (5) after drying, performing corrosion resistance test. The salt spray resistance is 30h and the adhesive force is 3 grade. As can be seen from comparison between example 1 and comparative example 1, the salt spray resistance of the coating material containing hemicellulose and cellulose is improved obviously, and the adhesion is improved by one level.
Example 2
In this embodiment, a water-based hemicellulose/cellulose/acrylic acid-epoxy resin coating specifically includes the following steps:
weighing 10 parts of acrylic acid modified epoxy resin coating, wherein the mass fraction of acrylic acid in the epoxy resin E-44 is 15%, and adding filler hemicellulose and cellulose according to the mass ratio of 2: 1. The filler accounts for 0.5 percent, 1 percent, 2 percent and 5 percent of the mass of the acrylic modified epoxy resin coating respectively. The mixture of the hemicellulose and the cellulose is added into deionized water for ultrasonic dispersion for 10min, so that the hemicellulose and the cellulose are uniformly dispersed in the deionized water, and then the uniformly dispersed solution is slowly added into the acrylic acid modified epoxy resin coating. And (3) keeping the mass solid content of the mixed coating to be 40%, continuing to magnetically stir for 6h, then performing negative-pressure defoaming for 15min, and then standing and defoaming for 12h to obtain the water-based hemicellulose/cellulose/acrylic acid-epoxy resin coating.
Uniformly coating the coating on No. 45 carbon steel, evaporating the solvent at room temperature for 12h, then putting the coating into a vacuum drying oven, drying at 40 ℃ for 48h, then heating to 90 ℃ and continuing to dry for 24 h. And (5) after drying, performing corrosion resistance test. The results are shown in Table 1:
TABLE 1
As can be seen from table 1, the coating material added with the mixture of hemicellulose and cellulose has the anti-corrosive performance that is improved and then reduced as the content of the mixture of hemicellulose and cellulose increases. But compared with the coating without the added filler, the anticorrosive performance of the coating is obviously improved within a proper range no matter how much the added filler is.
Example 3
In this embodiment, a water-based hemicellulose/cellulose/acrylic acid-epoxy resin coating specifically includes the following steps:
weighing 10 parts of acrylic acid modified epoxy resin coating, wherein the mass fraction of acrylic acid in the epoxy resin E-44 is 20%, and adding filler hemicellulose and cellulose according to the mass ratio of 3:1, 2:1, 1.5:1, 1:1, 1:1.5 and 1: 2. The filler mass respectively accounts for 2 percent of the acrylic modified epoxy resin coating. The mixture of the hemicellulose and the cellulose is added into deionized water for ultrasonic dispersion for 30min, so that the hemicellulose and the cellulose are uniformly dispersed in the deionized water, and then the uniformly dispersed solution is slowly added into the acrylic acid modified epoxy resin coating. And (3) keeping the mass solid content of the mixed coating to be 60%, continuing to magnetically stir for 6h, then performing negative-pressure defoaming for 15min, and then standing and defoaming for 12h to obtain the water-based hemicellulose/cellulose/acrylic acid-epoxy resin coating.
Uniformly coating the coating on No. 45 carbon steel, evaporating the solvent for 24h at room temperature, then putting the coating into a vacuum drying oven, drying for 24h at 60 ℃, then heating to 90 ℃, and continuing to dry for 12 h. And (5) after drying, performing corrosion resistance test. The results are shown in Table 2:
TABLE 2
As can be seen from table 2, when the content of the mixture of hemicellulose and cellulose is determined, the anticorrosive property of the coating is decreased as the proportion of hemicellulose is decreased, but the adhesion is slightly improved.
Example 4
In this embodiment, a water-based hemicellulose/cellulose/acrylic acid-epoxy resin coating specifically includes the following steps:
weighing 10 parts of acrylic acid modified epoxy resin coating, wherein the epoxy resin is epoxy resin E-12, epoxy resin E-20, epoxy resin E-44 and epoxy resin E-51, the mass fraction of acrylic acid in the epoxy resin (E-12, E-20, E-44 and E-51) is 15%, and adding filler hemicellulose and cellulose according to the mass ratio of 2: 1. The filler accounts for 2 percent of the mass of the acrylic modified epoxy resin coating. The mixture of the hemicellulose and the cellulose is added into deionized water for ultrasonic dispersion for 30min, so that the hemicellulose and the cellulose are uniformly dispersed in the deionized water, and then the uniformly dispersed solution is slowly added into the acrylic acid modified epoxy resin coating. And (3) keeping the mass solid content of the mixed coating to be 30%, continuing to magnetically stir for 6h, then performing ultrasonic defoaming for 15min, and then standing and defoaming for 12h to obtain the water-based hemicellulose/cellulose/acrylic acid-epoxy resin coating.
Uniformly coating the coating on No. 45 carbon steel, evaporating the solvent at room temperature for 24h, then putting the coating into a vacuum drying oven, drying at 60 ℃ for 48h, then heating to 80 ℃ and continuing to dry for 24 h. And (5) after drying, performing corrosion resistance test. The results are shown in Table 3:
comparative example 2
Weighing 10 parts of acrylic acid modified epoxy resin coating, wherein the epoxy resin is epoxy resin E-12, epoxy resin E-20, epoxy resin E-44 and epoxy resin E-51, and the mass fraction of acrylic acid in the epoxy resin (E-12, E-20, E-44 and E-51) is 15%, slowly adding deionized water into the epoxy resin coating, controlling the mass solid content of the coating to be 30%, continuing to magnetically stir for 6h, then performing ultrasonic defoaming for 30min, and then standing and defoaming for 12h to obtain the aqueous hemicellulose/cellulose/acrylic acid-epoxy resin coating.
Uniformly coating the coating on No. 45 carbon steel, evaporating the solvent at room temperature for 24h, then putting the coating into a vacuum drying oven, drying at 40 ℃ for 48h, then heating to 80 ℃ and continuing to dry for 24 h. And (5) after drying, performing corrosion resistance test. The results are shown in Table 3:
TABLE 3
As can be seen from comparison between the example 4 and the comparative example 2, for different types of epoxy resins, after hemicellulose and cellulose are added as fillers, the corrosion resistance of the coating is obviously improved, and the adhesive force is also improved. The results show that the hemicellulose and the cellulose can improve the corrosion resistance of the epoxy resin E-44, and can also improve the corrosion resistance of different types of epoxy resins.
Example 5
In this embodiment, a water-based hemicellulose/cellulose/acrylic acid-epoxy resin coating specifically includes the following steps:
weighing 10 parts of acrylic acid modified epoxy resin coating, wherein the mass fraction of acrylic acid in the epoxy resin E-44 is 15%, and adding filler hemicellulose and cellulose according to the mass ratio of 2: 1. The filler mass respectively accounts for 2 percent of the acrylic modified epoxy resin coating. The mixture of the hemicellulose and the cellulose is added into deionized water for ultrasonic dispersion for 30min, so that the hemicellulose and the cellulose are uniformly dispersed in the deionized water, and then the uniformly dispersed solution is slowly added into the acrylic acid modified epoxy resin coating. And (3) respectively keeping the mass solid contents of the mixed coating at 10%, 30%, 40% and 60%, continuing to magnetically stir for 6 hours, then performing ultrasonic defoaming for 15 minutes, and then standing and defoaming for 12 hours to obtain the water-based hemicellulose/cellulose/acrylic acid-epoxy resin coating.
Uniformly coating the coating on No. 45 carbon steel, evaporating the solvent at room temperature for 24h, then putting the coating into a vacuum drying oven, drying at 60 ℃ for 48h, then heating to 80 ℃ and continuing to dry for 24 h. And (5) after drying, performing corrosion resistance test. The results are shown in Table 4:
TABLE 4
As can be seen from Table 4, as the mass solids content of the coating decreased, the corrosion resistance increased first and then decreased. The corrosion resistance reaches the maximum value when the mass solid content is 30 percent, and reaches 130 h.
Claims (3)
1. A method for preparing a water-based hemicellulose/cellulose/acrylic acid-epoxy resin coating comprises the following specific steps:
(1) firstly, modifying epoxy resin with acrylic acid to obtain an acrylic acid-epoxy resin coating, wherein the acrylic acid accounts for 10-20% of the mass of the epoxy resin in the acrylic acid-epoxy resin coating; then, filler hemicellulose and cellulose are mixed and ultrasonically dispersed in deionized water, and the filler accounts for 0.5 to 5 mass percent of the acrylic acid-epoxy resin coating and is added into the acrylic acid-epoxy resin coating to obtain a mixed coating; wherein the mass solid content of the mixed coating is controlled to be 10-60 percent; the mass ratio of the hemicellulose to the cellulose is (0.5-3): 1;
(2) and (3) defoaming the mixed coating to obtain the aqueous hemicellulose/cellulose/acrylic acid-epoxy resin coating.
2. The method according to claim 1, wherein the epoxy resin in the epoxy resin modified with acrylic acid in step (1) is epoxy resin E-12, epoxy resin E-20, epoxy resin E-44 or epoxy resin E-51.
3. The method of claim 1, wherein the defoaming treatment method is one or two of standing, negative pressure and ultrasonic defoaming.
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