CN114989711A - Glass fiber reinforced plastic protective paint based on fluorine-containing hydroxypropyl resin and preparation method thereof - Google Patents
Glass fiber reinforced plastic protective paint based on fluorine-containing hydroxypropyl resin and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a glass fiber reinforced plastic protective paint based on fluorine-containing hydroxypropyl resin and a preparation method thereof; the protective paint is prepared to realize one-time coating, so that the coating and labor cost are saved, the time efficiency is improved, and the energy consumption is reduced; the coating formed by the protective paint has good alkali resistance, and the problem that the glass fiber reinforced plastic is not alkali-resistant is solved; the film forming substance in the coating film formed by the protective paint is fluorine-containing hydroxypropyl secondary dispersion, so that the weather resistance is improved; the mica sheet modified by cations is rich in polar groups such as hydroxyl, amino and the like, can realize uniform distribution and uniform orientation in fluorine-containing hydroxypropyl resin with higher glass transition temperature, and improves the barrier property of the glass fiber reinforced plastic protective paint through the labyrinth effect; the N, N-carbonyl diimidazole is used as a coupling agent to prepare konjac glucomannan grafted polyethyleneimine which is used as a cationic polymer to modify mica, so that the wettability of the protective paint to a base material, alkali resistance and weather resistance are further improved.
Description
Technical Field
The invention relates to the field of glass fiber reinforced plastic protective paint, in particular to glass fiber reinforced plastic protective paint based on fluorine-containing hydroxypropyl resin and a preparation method thereof.
Background
The glass fiber reinforced plastic is generally a fiber reinforced plastic prepared by reinforcing a matrix of unsaturated polyester, epoxy resin and phenolic resin with glass fibers, and is a reinforced plastic taking glass fibers or products thereof as reinforcing materials. In the existing market, the glass fiber reinforced plastics are widely applied to the preparation raw materials of storage tanks such as reaction tanks, anticorrosion storage tanks, chemical storage tanks, transportation storage tanks, food tanks and fire-fighting tanks. However, because of the severe service environment, the glass fiber reinforced plastic is exposed to the atmospheric environment for a long time, and the performance of the glass fiber reinforced plastic is easily reduced under the action of ultraviolet rays, wind, sand, rain, snow, chemical media, mechanical stress and the like, so that the glass fiber reinforced plastic is aged. Therefore, the coating must be coated outside the glass fiber reinforced plastic to achieve the effects of protecting the glass fiber reinforced plastic and prolonging the service life. At present, the external coating of the glass fiber reinforced plastic is mainly paint, and is mostly double-coating paint combining a double-component epoxy primer and a double-component acrylic finish.
However, the existing double-coating paint coating has the following problems: firstly, a large amount of solvent is volatilized, the VOC is high, and the environment is not protected; secondly, the long-term contact has influence on the health of constructors; the three-double coating paint is coated twice, and the coating and the labor cost are higher.
Disclosure of Invention
The invention aims to provide a glass fiber reinforced plastic protective paint based on fluorine-containing hydroxypropyl resin and a preparation method thereof, and aims to solve the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme:
a glass fiber reinforced plastic protective paint based on fluorine-containing hydroxypropyl resin is prepared by compounding glass fiber reinforced plastic colored paint and a curing agent in parts by weight; the glass fiber reinforced plastic colored paint comprises the following components in percentage by weight: 10-15 parts of deionized water, 1-3 parts of dispersing agent, 0.2-0.5 part of defoaming agent, 5-15 parts of barium sulfate filler, 5-20 parts of pigment, 50-65 parts of fluorine-containing hydroxyl acrylic acid, 0.1-0.3 part of base material wetting agent, 0.2-0.5 part of flatting agent, 0.2-0.4 part of polyurethane thickener and 0.5-1 part of rheological agent.
Further, the curing agent is obtained by compounding hydrophilic sulfonate modified isocyanate, isophorone diisocyanate, lipophilic isocyanate and propylene glycol diacetate according to the mass ratio of 1:1:1: 1.
The hydrophilic sulfonate modified isocyanate is kesichuang 2655; isophorone diisocyanate is kesichuang 401-70; the lipophilic isocyanate was 3900 kostew propylene glycol diacetate as dow PGDA.
Furthermore, the mass ratio of the glass fiber reinforced plastic colored paint to the curing agent is (6-7) to 1.
Further, the defoaming agent is BYK 028; the substrate wetting agent is digao 4100; the leveling agent is BYK 280; the polyurethane thickener is Zhanxin 6388; the dispersant is HP2361 (Callosa officinalis); the rheological agent is 5020W hamming.
Furthermore, the pigment and the filler are cation modified mica.
The invention provides a fluorine-containing hydroxypropyl resin-based glass fiber reinforced plastic protective paint and a preparation method thereof. The glass protective paint prepared by the invention is coated on glass fiber reinforced plastic: 1. the primer and the primer are coated once, so that the surface effect and performance requirements of two-time coating of epoxy and hydroxypropyl coatings can be met, the coating and labor cost can be saved, the time efficiency can be improved, and the energy consumption can be reduced; 2. the glass fiber reinforced plastic is not alkali-resistant, and after the coating is coated, a coating film has good alkali resistance, so that the glass fiber reinforced plastic is well protected in an alkali environment. 3. The film-forming material in the coating is fluorine-containing hydroxypropyl secondary dispersion, so that the weather resistance is improved. 4. Has wide application prospect.
According to the invention, a three-dimensional structure is formed by crosslinking and curing fluorine-containing hydroxypropyl resin, so that the barrier property of the glass protective paint is improved; and the crystallization degree and the glass transition temperature of the coating matrix resin can affect the barrier effect of the protective paint, because the protective paint needs to be added with plasticizers during processing to obtain good flexibility, but at the same time, the plasticizers are extremely easy to combine with pigment molecules under the high-temperature and pressure environment and cause the pigment molecules to migrate. Therefore, the pigment in the protective color paint is controlled to be cation modified mica, and the addition amount is controlled, so that the barrier capability of the protective glass fiber reinforced plastic paint is improved, and the easy cracking property of the coating is improved.
Mica is added into fluorine-containing hydroxypropyl resin as a flaky nano filler to obtain the organic/inorganic composite barrier coating. By introducing the highly oriented and overlapped multi-dimensional nano flaky materials into the coating matrix resin and forming a labyrinth effect, the migration of small molecules is better prevented, and the barrier effect of the glass protective paint is further improved.
Further, the pigment is cation modified mica, and the preparation method comprises the following steps: preparing a water solution with the mass concentration of 10% by using a cationic polymer and deionized water, adding sodium hydroxide to adjust the pH value to 7.8-8.2, adding mica to perform ultrasonic dispersion for 5-8min, heating to 68-72 ℃, stirring for 35-38min, performing suction filtration washing and drying, transferring to a dryer containing glutaraldehyde for 10-11h, taking out, and drying again to obtain the cation modified mica.
Furthermore, the mass ratio of the cationic polymer to the mica to the glutaraldehyde is 1:2: 3.
In order to realize uniform dispersion of the mica sheet in the fluorine-containing hydroxypropyl resin, the mica sheet is modified by using a cationic polymer with amino groups, compared with pure mica, the amino groups of the cationic polymer can be protonated and positively charged in a weak alkaline solution, and the surface of the mica sheet is negatively charged in an alkaline solution. Therefore, in the modification process, cationic polymer molecules are firstly adsorbed on the surface of mica through electrostatic interaction, and then hydroxyl and amine groups are crosslinked by glutaraldehyde to realize firm attachment and surface modification of the mica.
The introduction of polar groups such as hydroxyl groups, amino groups and the like is favorable for enhancing the interaction between the flaky mica filler and the acrylic resin and promoting the uniform dispersion of the mica sheet in the coating.
The thickness of the coating of the glass fiber reinforced plastic protective paint is limited to be 10-12 mu m, so that the complete barrier of the substrate layer can be realized, and the mechanical property of a coating formed by the glass fiber reinforced plastic protective paint cannot be adversely affected.
Further, the preparation of the cationic polymer comprises the following steps:
(1) swelling konjac glucomannan in deionized water, boiling for 3h, filtering, rotary-steaming, concentrating, washing with ethanol for 3-5 times, adding deionized water, chloroform and n-butanol, dialyzing, intercepting molecular weight by 10-12kDa, and freeze drying to obtain purified konjac glucomannan;
(2) stirring purified konjac glucomannan and deionized water at 65-70 ℃ for 2-3 h; adding sulfuric acid, stirring at 55-60 deg.C for 1-2h, cooling, neutralizing with sodium bicarbonate solution, dialyzing in deionized water for 20-22h, and lyophilizing to obtain purified and degraded konjac glucomannan;
(3) dissolving purified and degraded konjac glucomannan in dimethyl sulfoxide, stirring for 2-3h at 55-60 ℃, cooling to 18-25 ℃, adding N, N' -carbonyl diimidazole, and reacting for 1-2h to obtain activated konjac glucomannan; dissolving polyethyleneimine in dimethyl sulfoxide, adding activated konjac glucomannan, stirring for 4-5h, precipitating with anhydrous ethanol, cleaning, dissolving in deionized water, dialyzing, and concentrating by rotary evaporation, and freeze drying to obtain the cationic polymer.
Further, the mass ratio of the purified and degraded konjac glucomannan to the N, N' -carbonyl diimidazole is 1:1: 2.
A preparation method of glass fiber reinforced plastic protective paint based on fluorine-containing hydroxypropyl resin comprises the following steps:
s1: mixing fluorine-containing hydroxyl acrylic acid, deionized water, a dispersing agent, a defoaming agent, a barium sulfate filler, a base material wetting agent, a leveling agent and a rheological agent, stirring for 3-8min at 800rpm of 600-;
s2: compounding hydrophilic sulfonate modified isocyanate, isophorone diisocyanate, lipophilic isocyanate and propylene glycol diacetate to obtain a curing agent;
s3: mixing the glass fiber reinforced plastic colored paint and the curing agent, and stirring for 15-25min at 1000-1200rpm to obtain the glass fiber reinforced plastic protective paint based on fluorine-containing hydroxypropyl resin.
The konjac glucomannan is a natural neutral polysaccharide with good biocompatibility and degradation performance, the structure is rich in hydroxyl groups, modification and modification are easy, and the amino-rich cationic polymer with good biological safety is obtained; therefore, it is necessary to purify and degrade it before it is used in the grafting reaction.
The invention has the beneficial effects that:
the invention provides a fluorine-containing hydroxypropyl resin-based glass fiber reinforced plastic protective paint and a preparation method thereof, and the obtained glass fiber reinforced plastic protective paint has low energy consumption, excellent weather resistance and alkali resistance;
the protective paint prepared by the invention realizes one-time coating, saves the coating and labor cost, improves the time efficiency and reduces the energy consumption; the coating formed by the protective paint has good alkali resistance, and the problem that the glass fiber reinforced plastic is not alkali-resistant is solved; the film forming substance in the coating film formed by the protective paint is fluorine-containing hydroxypropyl secondary dispersion, so that the weather resistance is improved;
the glass fiber reinforced plastic protective paint prepared by using fluorine-containing hydroxypropyl resin with higher glass transition temperature as a matrix and using cation modified mica as a filler has good barrier effect. The film forming property, the adhesive force and the flexibility of the glass fiber reinforced plastic protective paint are further improved; the mica sheet modified by cations is rich in polar groups such as hydroxyl, amino and the like, can realize uniform distribution and uniform orientation in fluorine-containing hydroxypropyl resin, and improves the barrier property of the glass fiber reinforced plastic protective paint through the labyrinth effect;
the N, N-carbonyl diimidazole is used as a coupling agent to prepare konjac glucomannan grafted polyethyleneimine which is used as a cationic polymer to modify mica, so that the wettability of the protective paint to a base material, alkali resistance and weather resistance are further improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that, if directional indications such as up, down, left, right, front, and back … … are involved in the embodiment of the present invention, the directional indications are only used to explain the relative positional relationship, movement, and the like between the following components in a specific posture, and if the specific posture is changed, the directional indications are changed accordingly. In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention.
The technical solutions of the present invention are further described in detail with reference to the following specific examples, which should be understood as merely illustrative and not limitative.
Example 1
A preparation method of glass fiber reinforced plastic protective paint based on fluorine-containing hydroxypropyl resin comprises the following steps:
s1: mixing fluorine-containing hydroxyl acrylic acid, deionized water, a dispersing agent, a defoaming agent, a barium sulfate filler, a base material wetting agent, a leveling agent and a rheological agent, stirring for 8min at 600rpm, adding a pigment and a polyurethane thickener, and stirring for 20min at 900rpm to obtain glass fiber reinforced plastic colored paint;
s2: compounding hydrophilic sulfonate modified isocyanate, isophorone diisocyanate, lipophilic isocyanate and propylene glycol diacetate to obtain a curing agent;
the glass fiber reinforced plastic colored paint comprises the following components in parts by weight: 10 parts of deionized water, 1 part of dispersing agent, 0.2 part of defoaming agent, 5 parts of barium sulfate filler, 5 parts of pigment, 50 parts of fluorine-containing hydroxyl acrylic acid, 0.1 part of base material wetting agent, 0.2 part of flatting agent, 0.2 part of polyurethane thickener and 0.5 part of rheological agent;
the curing agent is obtained by compounding hydrophilic sulfonate modified isocyanate, isophorone diisocyanate, lipophilic isocyanate and propylene glycol diacetate according to the mass ratio of 1:1:1: 1;
the mass ratio of the glass fiber reinforced plastic colored paint to the curing agent is 6: 1; the hydrophilic sulfonate-modified isocyanate was 25 g;
the pigment is mica;
s3: mixing the glass fiber reinforced plastic colored paint and the curing agent, and stirring at 1000rpm for 25min to obtain the fluorine-containing hydroxypropyl resin-based glass fiber reinforced plastic protective paint.
Example 2
A preparation method of glass fiber reinforced plastic protective paint based on fluorine-containing hydroxypropyl resin comprises the following steps:
s1: mixing fluorine-containing hydroxyl acrylic acid, deionized water, a dispersing agent, a defoaming agent, a barium sulfate filler, a base material wetting agent, a leveling agent and a rheological agent, stirring for 5min at 700rpm, adding a pigment and a polyurethane thickener, and stirring for 15min at 1000rpm to obtain glass fiber reinforced plastic colored paint;
s2: compounding hydrophilic sulfonate modified isocyanate, isophorone diisocyanate, lipophilic isocyanate and propylene glycol diacetate to obtain a curing agent;
the glass fiber reinforced plastic colored paint comprises the following components in parts by weight: 12 parts of deionized water, 2 parts of dispersing agent, 0.3 part of defoaming agent, 10 parts of barium sulfate filler, 15 parts of pigment, 62 parts of fluorine-containing hydroxyl acrylic acid, 0.2 part of base material wetting agent, 0.3 part of flatting agent, 0.3 part of polyurethane thickener and 0.7 part of rheological agent;
the curing agent is obtained by compounding hydrophilic sulfonate modified isocyanate, isophorone diisocyanate, lipophilic isocyanate and propylene glycol diacetate according to the mass ratio of 1:1:1: 1; the hydrophilic sulfonate-modified isocyanate was 25 g;
the mass ratio of the glass fiber reinforced plastic colored paint to the curing agent is 6.5: 1;
the pigment is mica;
s3: mixing the glass fiber reinforced plastic colored paint and the curing agent, and stirring at 1100rpm for 20min to obtain the fluorine-containing hydroxypropyl resin-based glass fiber reinforced plastic protective paint.
Example 3
A preparation method of glass fiber reinforced plastic protective paint based on fluorine-containing hydroxypropyl resin comprises the following steps:
s1: mixing fluorine-containing hydroxyl acrylic acid, deionized water, a dispersing agent, a defoaming agent, a barium sulfate filler, a base material wetting agent, a leveling agent and a rheological agent, stirring at 800rpm for 3min, adding a pigment and a polyurethane thickener, and stirring at 1100rpm for 10min to obtain glass fiber reinforced plastic colored paint;
s2: compounding hydrophilic sulfonate modified isocyanate, isophorone diisocyanate, lipophilic isocyanate and propylene glycol diacetate to obtain a curing agent;
the glass fiber reinforced plastic colored paint comprises the following components in parts by weight: 15 parts of deionized water, 3 parts of a dispersing agent, 0.5 part of a defoaming agent, 15 parts of a barium sulfate filler, 20 parts of a pigment, 65 parts of fluorine-containing hydroxyl acrylic acid, 0.3 part of a base material wetting agent, 0.5 part of a leveling agent, 0.4 part of a polyurethane thickener and 1 part of a rheological agent;
the curing agent is obtained by compounding hydrophilic sulfonate modified isocyanate, isophorone diisocyanate, lipophilic isocyanate and propylene glycol diacetate according to the mass ratio of 1:1:1: 1; the hydrophilic sulfonate-modified isocyanate was 25 g;
the mass ratio of the glass fiber reinforced plastic colored paint to the curing agent is 7: 1;
the pigment is mica;
s3: mixing the glass fiber reinforced plastic colored paint and the curing agent, and stirring for 15min at 1200rpm to obtain the fluorine-containing hydroxypropyl resin-based glass fiber reinforced plastic protective paint.
Example 4
A preparation method of glass fiber reinforced plastic protective paint based on fluorine-containing hydroxypropyl resin comprises the following steps:
s1: mixing fluorine-containing hydroxyl acrylic acid, deionized water, a dispersing agent, a defoaming agent, a barium sulfate filler, a base material wetting agent, a leveling agent and a rheological agent, stirring for 8min at 600rpm, adding a pigment and a polyurethane thickener, and stirring for 20min at 900rpm to obtain glass fiber reinforced plastic colored paint;
s2: compounding hydrophilic sulfonate modified isocyanate, isophorone diisocyanate, lipophilic isocyanate and propylene glycol diacetate to obtain a curing agent;
the glass fiber reinforced plastic colored paint comprises the following components in parts by weight: 10 parts of deionized water, 1 part of dispersing agent, 0.2 part of defoaming agent, 5 parts of barium sulfate filler, 5 parts of pigment, 50 parts of fluorine-containing hydroxyl acrylic acid, 0.1 part of base material wetting agent, 0.2 part of flatting agent, 0.2 part of polyurethane thickener and 0.5 part of rheological agent;
the curing agent is obtained by compounding hydrophilic sulfonate modified isocyanate, isophorone diisocyanate, lipophilic isocyanate and propylene glycol diacetate according to the mass ratio of 1:1:1: 1;
the mass ratio of the glass fiber reinforced plastic colored paint to the curing agent is 6: 1;
the pigment is cation modified mica, and the preparation method comprises the following steps: preparing 2g of cationic polymer and deionized water into a 10% aqueous solution, adding sodium hydroxide to adjust the pH to 7.8, adding 4g of mica, ultrasonically dispersing for 5min, heating to 68 ℃, stirring for 38min, performing suction filtration, washing and drying, transferring to a dryer containing 6g of glutaraldehyde for 10h, taking out, and drying again to obtain cationic modified mica;
the preparation of the cationic polymer comprises the following steps:
(1) swelling konjac glucomannan in deionized water, boiling for 3h, filtering, performing rotary evaporation and concentration, washing with ethanol for 3 times, adding deionized water, chloroform and n-butanol, dialyzing, intercepting molecular weight of 10kDa, and freeze-drying to obtain purified konjac glucomannan;
(2) 1g of purified konjac glucomannan and 30mL of deionized water are taken and stirred for 3 hours at 65 ℃; adding 4mL of 12% sulfuric acid, stirring at 55 ℃ for 2h, cooling, neutralizing with sodium bicarbonate solution, dialyzing in deionized water for 20h, and freeze-drying to obtain purified and degraded konjac glucomannan;
(3) dissolving 400mg of purified and degraded konjac glucomannan in dimethyl sulfoxide, stirring for 3h at 55 ℃, cooling to 18 ℃, adding 400mg of N, N' -carbonyl diimidazole, and reacting for 2h to obtain activated konjac glucomannan; dissolving 0.8g of polyethyleneimine in dimethyl sulfoxide, adding activated konjac glucomannan, stirring for 4h, precipitating with absolute ethanol, cleaning, dissolving in deionized water, dialyzing, intercepting the molecular weight of 4kDa, performing rotary evaporation concentration, and freeze drying to obtain a cationic polymer;
s3: mixing the glass fiber reinforced plastic colored paint and the curing agent, and stirring at 1000rpm for 25min to obtain the fluorine-containing hydroxypropyl resin-based glass fiber reinforced plastic protective paint.
Example 5
A preparation method of glass fiber reinforced plastic protective paint based on fluorine-containing hydroxypropyl resin comprises the following steps:
s1: mixing fluorine-containing hydroxyl acrylic acid, deionized water, a dispersing agent, a defoaming agent, a barium sulfate filler, a base material wetting agent, a leveling agent and a rheological agent, stirring for 5min at 700rpm, adding a pigment and a polyurethane thickener, and stirring for 15min at 1000rpm to obtain glass fiber reinforced plastic colored paint;
s2: compounding hydrophilic sulfonate modified isocyanate, isophorone diisocyanate, lipophilic isocyanate and propylene glycol diacetate to obtain a curing agent;
the glass fiber reinforced plastic colored paint comprises the following components in parts by weight: 12 parts of deionized water, 2 parts of dispersing agent, 0.3 part of defoaming agent, 10 parts of barium sulfate filler, 15 parts of pigment, 62 parts of fluorine-containing hydroxyl acrylic acid, 0.2 part of base material wetting agent, 0.3 part of flatting agent, 0.3 part of polyurethane thickener and 0.7 part of rheological agent;
the curing agent is obtained by compounding hydrophilic sulfonate modified isocyanate, isophorone diisocyanate, lipophilic isocyanate and propylene glycol diacetate according to the mass ratio of 1:1:1: 1;
the mass ratio of the glass fiber reinforced plastic colored paint to the curing agent is 6.5: 1;
the pigment is cation modified mica, and the preparation method comprises the following steps: preparing 2g of cationic polymer and deionized water into 10% aqueous solution, adding sodium hydroxide to adjust the pH to 8, adding 4g of mica, performing ultrasonic dispersion for 7min, heating to 70 ℃, stirring for 36min, performing suction filtration, washing and drying, transferring to a dryer containing 6g of glutaraldehyde for 10.5h, taking out, and drying again to obtain cation modified mica;
the preparation of the cationic polymer comprises the following steps:
(1) swelling konjac glucomannan in deionized water, boiling for 3h, filtering, performing rotary evaporation and concentration, washing with ethanol for 4 times, adding deionized water, chloroform and n-butanol, dialyzing, intercepting the molecular weight of 11kDa, and freeze-drying to obtain purified konjac glucomannan;
(2) 1g of purified konjac glucomannan and 30mL of deionized water are stirred for 2.5 hours at 68 ℃; adding 4mL of 12% sulfuric acid, stirring at 58 ℃ for 1.5h, cooling, neutralizing with sodium bicarbonate solution, dialyzing in deionized water for 21h, and freeze-drying to obtain purified and degraded konjac glucomannan;
(3) dissolving 400mg of purified and degraded konjac glucomannan in dimethyl sulfoxide, stirring for 1.5h at 58 ℃, cooling to 20 ℃, adding 400mg of N, N' -carbonyldiimidazole, and reacting for 1.5h to obtain activated konjac glucomannan; dissolving 0.8g of polyethyleneimine in dimethyl sulfoxide, adding activated konjac glucomannan, stirring for 4.5h, precipitating with absolute ethanol, washing, dissolving in deionized water, dialyzing, intercepting the molecular weight of 4kDa, performing rotary evaporation concentration, and freeze drying to obtain a cationic polymer;
s3: mixing the glass fiber reinforced plastic colored paint and the curing agent, and stirring at 1100rpm for 20min to obtain the fluorine-containing hydroxypropyl resin-based glass fiber reinforced plastic protective paint.
Example 6
A preparation method of glass fiber reinforced plastic protective paint based on fluorine-containing hydroxypropyl resin comprises the following steps:
s1: mixing fluorine-containing hydroxyl acrylic acid, deionized water, a dispersing agent, a defoaming agent, a barium sulfate filler, a base material wetting agent, a leveling agent and a rheological agent, stirring at 800rpm for 3min, adding a pigment and a polyurethane thickener, and stirring at 1100rpm for 10min to obtain glass fiber reinforced plastic colored paint;
s2: compounding hydrophilic sulfonate modified isocyanate, isophorone diisocyanate, lipophilic isocyanate and propylene glycol diacetate to obtain a curing agent;
the glass fiber reinforced plastic colored paint comprises the following components in parts by weight: 15 parts of deionized water, 3 parts of dispersing agent, 0.5 part of defoaming agent, 15 parts of barium sulfate filler, 20 parts of pigment, 65 parts of fluorine-containing hydroxyl acrylic acid, 0.3 part of base material wetting agent, 0.5 part of flatting agent, 0.4 part of polyurethane thickener and 1 part of rheological agent;
the curing agent is obtained by compounding hydrophilic sulfonate modified isocyanate, isophorone diisocyanate, lipophilic isocyanate and propylene glycol diacetate according to the mass ratio of 1:1:1: 1; the hydrophilic sulfonate-modified isocyanate was 25 g;
the mass ratio of the glass fiber reinforced plastic colored paint to the curing agent is 7: 1;
the pigment is cation modified mica, and the preparation method comprises the following steps: preparing 2g of cationic polymer and deionized water into 10% aqueous solution, adding sodium hydroxide to adjust the pH to 8.2, adding 4g of mica, performing ultrasonic dispersion for 5-8min, heating to 72 ℃, stirring for 35min, performing suction filtration, washing and drying, transferring to a dryer containing 6g of glutaraldehyde for 10-11h, taking out, and drying again to obtain cation modified mica;
the preparation of the cationic polymer comprises the following steps:
(1) swelling konjac glucomannan in deionized water, boiling for 3h, filtering, performing rotary evaporation and concentration, washing with ethanol for 5 times, adding deionized water, chloroform and n-butanol, dialyzing, intercepting molecular weight of 12kDa, and freeze drying to obtain purified konjac glucomannan;
(2) 1g of purified konjac glucomannan and 30mL of deionized water are stirred for 2 hours at 70 ℃; adding 4mL of 12% sulfuric acid, stirring at 60 ℃ for 1h, cooling, neutralizing with sodium bicarbonate solution, dialyzing in deionized water for 22h, and freeze-drying to obtain purified and degraded konjac glucomannan;
(3) dissolving 400mg of purified and degraded konjac glucomannan in dimethyl sulfoxide, stirring for 2h at 60 ℃, cooling to 25 ℃, adding 400mg of N, N' -carbonyl diimidazole, and reacting for 2h to obtain activated konjac glucomannan; dissolving 0.8g of polyethyleneimine in dimethyl sulfoxide, adding activated konjac glucomannan, stirring for 5 hours, precipitating with absolute ethanol, cleaning, dissolving in deionized water, dialyzing, and performing rotary evaporation concentration and freeze drying to obtain a cationic polymer, wherein the molecular weight of the cationic polymer is 4 kDa;
s3: mixing the glass fiber reinforced plastic colored paint and the curing agent, and stirring for 15min at 1200rpm to obtain the fluorine-containing hydroxypropyl resin-based glass fiber reinforced plastic protective paint.
Comparative example 1
The comparative example 4 was used, and the other steps were carried out normally, by replacing the fluorine-containing hydroxyacrylic acid with hydroxyacrylic acid.
Comparative example 2
Example 4 was used as a control, and the other steps were normal without adding a cationic polymer.
Raw material grades referred to in examples 1-6, comparative examples 1-2: the hydrophilic sulfonate modified isocyanate is kesichuang 2655; isophorone diisocyanate is kesichuang 401-70; the lipophilic isocyanate is 3900 kosmon; the propylene glycol diacetate is Dow PGDA;
the defoaming agent is BYK 028; the substrate wetting agent is digao 4100; the leveling agent is BYK 280; the polyurethane thickener is Zhanxin 6388; dispersant HP2361 glitter; the rheological agent is 5020W hamming.
And (3) performance testing: the glass fiber reinforced plastic protective paint prepared in examples 1-6 and comparative examples 1-2 was subjected to performance test: the hardness is referred to GB/T6739; the adhesive force refers to GB/T9286; solvent-resistant wiping reference GB/T23989; the water resistance is referred to GB/T1733; the acid resistance and the alkali resistance are referred to GB/T9274; the wet cold heat cycle refers to GB/T2423.4; the humidity and heat resistance is referenced to GB/T1740; the salt fog resistance is referred to GB/T1771; the data are shown in Table 1;
TABLE 1
The protective paint prepared by the invention realizes one-time coating, saves coating and labor cost, improves time efficiency and reduces energy consumption; the coating formed by the protective paint has good alkali resistance, and the problem that the glass fiber reinforced plastic is not alkali-resistant is solved; the film forming substance in the coating film formed by the protective paint is fluorine-containing hydroxypropyl secondary dispersion, so that the weather resistance is improved;
as shown by comparison between example 4 and examples 2 and comparative example 1, the glass fiber reinforced plastic protective paint prepared by using the fluorine-containing hydroxypropyl resin with higher glass transition temperature as the matrix and the cation modified mica as the filler has good barrier effect. The film forming property, the adhesive force and the flexibility of the glass fiber reinforced plastic protective paint are further improved; the mica sheet modified by cations is rich in polar groups such as hydroxyl, amino and the like, can realize uniform distribution and uniform orientation in fluorine-containing hydroxypropyl resin, and improves the barrier property of the glass fiber reinforced plastic protective paint through the labyrinth effect;
comparing example 4 with example 2 and comparative example 2, it can be seen that konjac glucomannan grafted polyethyleneimine prepared by using N, N-carbonyl diimidazole as a coupling agent is used as a cationic polymer to modify mica, so as to further improve the wettability, alkali resistance and weather resistance of the protective paint to the base material.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and all modifications and equivalents of the present invention, which are made by the present specification and directly/indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (10)
1. The glass fiber reinforced plastic protective paint based on fluorine-containing hydroxypropyl resin is characterized in that: the glass fiber reinforced plastic protective paint is obtained by compounding glass fiber reinforced plastic colored paint and a curing agent; the glass fiber reinforced plastic colored paint comprises the following components in parts by weight: 10-15 parts of deionized water, 1-3 parts of dispersing agent, 0.2-0.5 part of defoaming agent, 5-15 parts of barium sulfate filler, 5-20 parts of pigment, 50-65 parts of fluorine-containing hydroxyl acrylic acid, 0.1-0.3 part of base material wetting agent, 0.2-0.5 part of flatting agent, 0.2-0.4 part of polyurethane thickener and 0.5-1 part of rheological agent.
2. The fluorine-containing hydroxypropyl resin-based glass fiber reinforced plastic protective paint according to claim 1, characterized in that: the curing agent is obtained by compounding hydrophilic sulfonate modified isocyanate, isophorone diisocyanate, lipophilic isocyanate and propylene glycol diacetate according to the mass ratio of 1:1:1: 1.
3. The glass fiber reinforced plastic protective paint based on fluorine-containing hydroxypropyl resin as claimed in claim 1, is characterized in that: the mass ratio of the glass fiber reinforced plastic colored paint to the curing agent is (6-7) to 1.
4. The glass fiber reinforced plastic protective paint based on fluorine-containing hydroxypropyl resin as claimed in claim 1, is characterized in that: the pigment is cation modified mica, and the preparation method comprises the following steps: mixing and stirring a cationic polymer and deionized water, adding sodium hydroxide to adjust the pH value, adding mica, performing ultrasonic dispersion for 5-8min, heating to 68-72 ℃, stirring for 35-38min, performing suction filtration, washing and drying, transferring to a dryer containing glutaraldehyde for 10-11h, taking out, and drying again to obtain the cationic modified mica.
5. The glass fiber reinforced plastic protective paint based on fluorine-containing hydroxypropyl resin as claimed in claim 4, is characterized in that: the mass ratio of the cationic polymer to the mica to the glutaraldehyde is 1:2: 3.
6. The glass fiber reinforced plastic protective paint based on fluorine-containing hydroxypropyl resin as claimed in claim 4, is characterized in that: the pH is 7.8-8.2.
7. The glass fiber reinforced plastic protective paint based on fluorine-containing hydroxypropyl resin as claimed in claim 4, is characterized in that: the preparation of the cationic polymer comprises the following steps: dissolving purified and degraded konjac glucomannan in dimethyl sulfoxide, stirring for 2-3h at 55-60 ℃, cooling to 18-25 ℃, adding N, N' -carbonyl diimidazole, and reacting for 1-2h to obtain activated konjac glucomannan; dissolving polyethyleneimine in dimethyl sulfoxide, adding activated konjac glucomannan, stirring for 4-5h, precipitating with anhydrous ethanol, cleaning, dissolving in deionized water, dialyzing, and concentrating by rotary evaporation, and freeze drying to obtain cationic polymer.
8. The glass fiber reinforced plastic protective paint based on fluorine-containing hydroxypropyl resin as claimed in claim 7, is characterized in that: the mass ratio of the purified and degraded konjac glucomannan, the N, N' -carbonyl diimidazole and the polyethyleneimine is 1:1: 2.
9. The glass fiber reinforced plastic protective paint based on fluorine-containing hydroxypropyl resin as claimed in claim 7, is characterized in that: the preparation method of the purified and degraded konjac glucomannan comprises the following steps:
(1) swelling konjac glucomannan in deionized water, boiling for 3h, filtering, rotary-steaming, concentrating, washing with ethanol for 3-5 times, adding deionized water, chloroform and n-butanol, dialyzing, intercepting molecular weight by 10-12kDa, and freeze drying to obtain purified konjac glucomannan;
(2) stirring purified konjac glucomannan and deionized water at 65-70 ℃ for 2-3 h; adding sulfuric acid, stirring at 55-60 deg.C for 1-2 hr, cooling, neutralizing with sodium bicarbonate solution, dialyzing in deionized water for 20-22 hr, and lyophilizing to obtain purified and degraded konjac glucomannan.
10. The preparation method of the fluorine-containing hydroxypropyl resin-based glass fiber reinforced plastic protective paint according to any one of claims 1 to 9, characterized in that: the method comprises the following steps:
s1: mixing fluorine-containing hydroxyl acrylic acid, deionized water, a dispersing agent, a defoaming agent, a barium sulfate filler, a base material wetting agent, a leveling agent and a rheological agent, stirring for 3-8min at 800rpm of 600-;
s2: compounding hydrophilic sulfonate modified isocyanate, isophorone diisocyanate, lipophilic isocyanate and propylene glycol diacetate to obtain a curing agent;
s3: mixing the glass fiber reinforced plastic colored paint and the curing agent, and stirring for 15-25min at 1000-1200rpm to obtain the glass fiber reinforced plastic protective paint based on fluorine-containing hydroxypropyl resin.
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