CN115746669B - Epoxy resin anti-corrosion floor paint and preparation method thereof - Google Patents
Epoxy resin anti-corrosion floor paint and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an epoxy resin anti-corrosion floor paint and a preparation method thereof, belonging to the technical field of floor paint, and comprising a component A and a component B; the mass ratio of the component A to the component B is 110-120:100; the component A comprises the following components: 75-80 parts of epoxy resin and 10-15 parts of deionized water; the component B comprises: 20-30 parts of deionized water, 30-35 parts of curing agent, 10-12 parts of modified filler, 1-2 parts of defoamer and 1-2 parts of dispersing agent; and mixing according to a proportion to obtain the epoxy resin anti-corrosion floor paint. Compared with the modification treatment by only relying on the silane coupling agent, the modified filler is more beneficial to improving the dispersion effect of the modified filler in the polymer, meanwhile, after the mixed monomer treatment, the modified filler, the curing agent and the epoxy resin are mutually penetrated and intertwined to form a cross-linked reticular polymer blend, so that a more stable structure is formed, the function of the filler is fully exerted, and the wear resistance is improved.
Description
Technical Field
The invention belongs to the technical field of floor paint, and particularly relates to epoxy resin anti-corrosion floor paint and a preparation method thereof.
Background
The epoxy resin floor paint is a high-strength wear-resistant attractive floor paint, and the epoxy resin floor paint used in the industries of electroplating, chemical engineering and the like has higher requirements on the corrosion resistance; meanwhile, the epoxy resin floor paint has poor scratch resistance, and can show obvious scratches when suffering from high hardness or sharp objects in the use process, thereby having a certain influence on the attractiveness of the epoxy resin floor paint.
In the prior art, rigid particles are generally added to improve the performance of the epoxy resin, when the epoxy resin is deformed by external force, most of energy in the epoxy resin is absorbed by the rigid particles, so that microcracks are generated, silver grains can be passivated and blocked by the nano particles in the silver grain expansion process, so that stagnation is generated, the purpose of improving the performance is achieved, and the rigid particles are generally poor in dispersibility due to the nano structure and compatibility with the epoxy resin, so that agglomeration and fault often exist in a resin layer.
Disclosure of Invention
The invention aims to provide an epoxy resin anti-corrosion floor paint and a preparation method thereof, which are used for solving the problems in the background technology.
The aim of the invention can be achieved by the following technical scheme:
an epoxy resin anti-corrosion floor paint comprises a component A and a component B; the mass ratio of the component A to the component B is 110-120:100;
the component A comprises the following components: 75-80 parts of epoxy resin and 10-15 parts of deionized water;
the component B comprises: 20-30 parts of deionized water, 30-35 parts of curing agent, 10-12 parts of modified filler, 1-2 parts of defoamer and 1-2 parts of dispersing agent;
the modified filler is prepared by the following steps:
adding a silane coupling agent into cyclohexane, then adding hydrotalcite, carrying out ultrasonic dispersion, heating, refluxing and stirring for 6 hours, cooling to room temperature after stirring is finished, carrying out centrifugal separation, washing with ethanol, and drying to obtain a pretreated filler;
and step two, mixing the pretreated filler with deionized water, adding a mixed monomer and ceric ammonium nitrate, setting the temperature to 60 ℃, stirring and reacting for 10 hours, and filtering and drying after the reaction is finished to obtain the modified filler.
Further, the silane coupling agent in the step one is formed by mixing gamma-aminopropyl triethoxysilane, gamma-methacryloxypropyl trimethoxysilane and the like in mass; the dosage ratio of the silane coupling agent, hydrotalcite and cyclohexane is 0.15g:3g:150mL. The modified filler is prepared by taking hydrotalcite as a matrix, treating the hydrotalcite by a silane coupling agent, introducing double bonds and amino groups into the structure of the hydrotalcite, and then carrying out polymerization reaction with a mixed monomer.
Further, the mixed monomer in the second step is obtained by mixing two or more than two of acrylic acid, methacrylic acid, 2-ethyl acrylic acid and 3-methoxy acrylic acid according to any proportion; the dosage ratio of the pretreatment filler to the deionized water is 1;100mL; the mass ratio of the mixed monomer to the pretreated filler is 2:5, a step of; the addition amount of the ammonium cerium nitrate is 15% of the mass of the pretreated filler.
Further, the curing agent is prepared by the following steps:
step S1, adding cystine and potassium hydroxide into absolute ethyl alcohol, stirring for 5min at 50 ℃, then heating to 55 ℃, adding vanillin, stirring for 30min, washing with diethyl ether after the reaction is finished, and recrystallizing with ethanol to obtain a Schiff base-containing intermediate;
s2, adding the Schiff base-containing intermediate and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide into tetrahydrofuran, heating and refluxing for reaction for 12 hours, and cooling and filtering after the reaction is finished to obtain the curing agent. The phosphorus-containing element is introduced into the curing agent through 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), so that the flame retardant property of the cured epoxy resin is improved, and meanwhile, in order to compensate the influence of the increase of the phosphorus content on the thermal stability of the epoxy resin, the P-H bond of DOPO and C=N bond of the DOPO are used as raw materials to prepare the curing agent through the reaction of the Schiff base-containing intermediate and the DOPO, and the curing agent can also be used as reactive flame retardant and has the advantages of no halogen, no smoke, no toxicity, migration resistance and the like.
The Schiff base-containing intermediate is prepared from cystine and vanillin serving as raw materials, disulfide bonds are introduced into the structure of the curing agent, the disulfide bonds can be broken under the conditions of stress and the like to form sulfur free radicals, so that sulfydryl is formed, external energy can be released in the changing process, the coating is prevented from being further damaged, the coating has stronger mechanical property, and the disulfide bonds can be formed again after the coating is damaged by external force, so that the self-repairing effect is realized.
Further, in the step S1, the molar ratio of cystine to vanillin is 1:1, a step of; the dosage ratio of cystine, potassium hydroxide and absolute ethanol is 2.4g:1g:50mL;
the dosage ratio of the schiff base intermediate, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and tetrahydrofuran in the step S2 is 5.4g:4.2g:100mL.
Further, the epoxy resin is selected from one or more of bisphenol a type epoxy resin, alicyclic epoxy resin, bisphenol F type epoxy resin or novolac epoxy resin.
Further, the defoamer is one of 1340 defoamer, 822 defoamer and 805 defoamer; the dispersing agent is one of 602N dispersing agent and 5040 dispersing agent.
Further, the particle size of the modified filler is 400-600 meshes.
The preparation method of the epoxy resin anti-corrosion floor paint comprises the following steps:
firstly, 75-80 parts of epoxy resin and 10-15 parts of deionized water are mixed according to parts by weight, and stirred and dispersed for 30-40min to obtain a component A; mixing 20-30 parts of deionized water, 30-35 parts of curing agent, 10-12 parts of modified filler, 1-2 parts of defoamer and 1-2 parts of dispersing agent, and stirring and dispersing for 40-50min to obtain a component B;
and secondly, mixing the component A and the component B according to the mass ratio to obtain the epoxy resin anti-corrosion floor paint.
The invention has the beneficial effects that:
in the process of preparing the epoxy resin anti-corrosion floor paint, hydrotalcite is used as a matrix of modified filler, particles are easy to agglomerate together when the added amount of the modified filler is excessive, the performance of the whole matrix cannot be improved, the method is more beneficial to improving the dispersion effect of the modified filler in a polymer compared with the modification treatment by only relying on a silane coupling agent, and meanwhile, after the treatment of mixed monomers, the modified filler, a curing agent and the epoxy resin are mutually penetrated and intertwined to form a cross-linked reticular polymer blend, so that a more stable structure is formed, the effect of the filler is fully exerted, and the wear resistance is improved.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
An epoxy resin anti-corrosion floor paint comprises a component A and a component B; the mass ratio of the component A to the component B is 110-120:100;
the component A comprises the following components: 75-80 parts of epoxy resin and 10-15 parts of deionized water;
the component B comprises: 20-30 parts of deionized water, 30-35 parts of curing agent, 10-12 parts of modified filler, 1-2 parts of defoamer and 1-2 parts of dispersing agent.
Example 1
Preparing modified filler:
adding a silane coupling agent into cyclohexane, then adding hydrotalcite, carrying out ultrasonic dispersion, heating, refluxing and stirring for 6 hours, cooling to room temperature after stirring is finished, carrying out centrifugal separation, washing with ethanol, and drying to obtain a pretreated filler; the silane coupling agent is formed by mixing gamma-aminopropyl triethoxysilane, gamma-methacryloxypropyl trimethoxysilane and the like in mass; the dosage ratio of the silane coupling agent, hydrotalcite and cyclohexane is 0.15g:3g:150mL
And step two, mixing the pretreated filler with deionized water, adding a mixed monomer and ceric ammonium nitrate, setting the temperature to 60 ℃, stirring and reacting for 10 hours, and filtering and drying after the reaction is finished to obtain the modified filler, wherein the particle size of the modified filler is 400-600 meshes. The mixed monomer is acrylic acid, methacrylic acid and the like which are mixed in an equimolar way, and the dosage ratio of the pretreatment filler to deionized water is 1;100mL; the mass ratio of the mixed monomer to the pretreated filler is 2:5, a step of; the addition amount of the ammonium cerium nitrate is 15% of the mass of the pretreated filler.
Example 2
Preparing modified filler:
adding a silane coupling agent into cyclohexane, then adding hydrotalcite, carrying out ultrasonic dispersion, heating, refluxing and stirring for 6 hours, cooling to room temperature after stirring is finished, carrying out centrifugal separation, washing with ethanol, and drying to obtain a pretreated filler; the silane coupling agent is formed by mixing gamma-aminopropyl triethoxysilane, gamma-methacryloxypropyl trimethoxysilane and the like in mass; the dosage ratio of the silane coupling agent, hydrotalcite and cyclohexane is 0.15g:3g:150mL
And step two, mixing the pretreated filler with deionized water, adding a mixed monomer and ceric ammonium nitrate, setting the temperature to 60 ℃, stirring and reacting for 10 hours, and filtering and drying after the reaction is finished to obtain the modified filler, wherein the particle size of the modified filler is 400-600 meshes. The mixed monomer is 2-ethyl acrylic acid and 3-methoxy acrylic acid which are mixed in an equimolar way, and the dosage ratio of the pretreatment filler to deionized water is 1;100mL; the mass ratio of the mixed monomer to the pretreated filler is 2:5, a step of; the addition amount of the ammonium cerium nitrate is 15% of the mass of the pretreated filler.
Example 3
Preparing a curing agent:
step S1, adding cystine and potassium hydroxide into absolute ethyl alcohol, stirring for 5min at 50 ℃, then heating to 55 ℃, adding vanillin, stirring for 30min, washing with diethyl ether after the reaction is finished, and recrystallizing with ethanol to obtain a Schiff base-containing intermediate; cystine and vanillin were obtained in a molar ratio of 1:1, a step of; the dosage ratio of cystine, potassium hydroxide and absolute ethanol is 2.4g:1g:50mL;
s2, adding the Schiff base-containing intermediate and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide into tetrahydrofuran, heating and refluxing for reaction for 12 hours, and cooling and filtering after the reaction is finished to obtain the curing agent. The dosage ratio of the Schiff base-containing intermediate, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and tetrahydrofuran is 5.4g:4.2g:100mL.
Comparative example 1
In comparison with example 3, the cystine was replaced by aspartic acid, and the rest of the raw materials and the preparation process were kept the same as in example 3.
Example 4
The preparation method of the epoxy resin anti-corrosion floor paint comprises the following steps:
firstly, 75 parts of bisphenol A epoxy resin and 10 parts of deionized water are mixed according to parts by weight, stirred and dispersed for 30 minutes to obtain a component A; mixing 20 parts of deionized water, 30 parts of the curing agent prepared in example 3, 10 parts of the modified filler prepared in example 1, 1 part of 1340 defoamer and 1 part of 602N dispersant, and stirring and dispersing for 40min to obtain a component B;
secondly, according to the mass ratio of 110:100 mixing the component A and the component B to obtain the epoxy resin anti-corrosion floor paint.
Example 5
The preparation method of the epoxy resin anti-corrosion floor paint comprises the following steps:
firstly, 75 parts of bisphenol A epoxy resin and 10 parts of deionized water are mixed according to parts by weight, stirred and dispersed for 30 minutes to obtain a component A; mixing 20 parts of deionized water, 30 parts of the curing agent prepared in example 3, 10 parts of the modified filler prepared in example 2, 1 part of 1340 defoamer and 1 part of 602N dispersant, and stirring and dispersing for 40min to obtain a component B;
secondly, according to the mass ratio of 110:100 mixing the component A and the component B to obtain the epoxy resin anti-corrosion floor paint.
Example 6
The preparation method of the epoxy resin anti-corrosion floor paint comprises the following steps:
firstly, mixing 80 parts by weight of bisphenol A epoxy resin and 15 parts by weight of deionized water, and stirring and dispersing for 40 minutes to obtain a component A; 30 parts of deionized water, 35 parts of the curing agent prepared in example 3, 12 parts of the modified filler prepared in example 2, 2 parts of 1340 defoamer and 2 parts of 602N dispersing agent are mixed, stirred and dispersed for 50min to obtain a component B;
secondly, according to the mass ratio of 120:100 mixing the component A and the component B to obtain the epoxy resin anti-corrosion floor paint.
Comparative example 2
In comparison with example 6, the modified filler was replaced by the pretreated filler prepared in example 2, and the remaining raw materials and preparation process were kept the same as in example 6.
Comparative example 3
In comparison with example 6, the curing agent was changed to the sample prepared in comparative example 1, and the remaining raw materials and the preparation process were kept the same as in example 6.
Performance tests were carried out on examples 4 to 6 and comparative examples 2 to 3, and abrasion resistance was tested according to the method of GB/T17682006 abrasion resistance test for color paint and varnish, test bars having dimensions of 150 mm. Times.6.5 mm. Times.3 mm; the combustion performance of the sample bar is measured by an oxygen index method under the specified test conditions (23+/-2 ℃), and the minimum oxygen concentration required for just maintaining combustion is measured in an oxygen-nitrogen mixed gas and expressed by the volume percentage of the oxygen content in the mixed gas; scratch the coating with the width of 30-70 mu m, then exposing at 37 ℃ to observe whether repairing is carried out;
the results are shown in Table 1:
TABLE 1
| Project | Example 4 | Example 5 | Example 6 | Comparative example 2 | Comparative example 3 |
| Wear resistance 750 g/500R/(g) | 0.0005 | 0.0004 | 0.0004 | 0.0029 | 0.0008 |
| Limiting oxygen index/(%) | 33.5 | 33.8 | 33.7 | 33.6 | 33.5 |
| Whether or not to repair | Is that | Is that | Is that | Is that | Whether or not |
As can be seen from Table 1, the prepared epoxy resin anti-corrosion floor paint has good wear resistance and certain flame retardance.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (5)
1. An epoxy resin anti-corrosion floor paint comprises a component A and a component B; the weight ratio of the component A to the component B is 110-120:100; the component A comprises the following components: 75-80 parts of epoxy resin and 10-15 parts of deionized water; the component B comprises: 20-30 parts of deionized water, 30-35 parts of curing agent, 10-12 parts of modified filler, 1-2 parts of defoamer and 1-2 parts of dispersing agent;
the modified filler is prepared by the following steps:
adding a silane coupling agent into cyclohexane, then adding hydrotalcite, carrying out ultrasonic dispersion, heating, refluxing and stirring for 6 hours, cooling to room temperature after stirring is finished, carrying out centrifugal separation, washing with ethanol, and drying to obtain a pretreated filler; the silane coupling agent is formed by mixing gamma-aminopropyl triethoxysilane, gamma-methacryloxypropyl trimethoxysilane and the like in mass;
step two, mixing the pretreated filler with deionized water, then adding a mixed monomer and ceric ammonium nitrate, setting the temperature to 60 ℃, stirring and reacting for 10 hours, and filtering and drying after the reaction is finished to obtain a modified filler; the mixed monomer is obtained by mixing two or more than two of acrylic acid, methacrylic acid, 2-ethyl acrylic acid and 3-methoxy acrylic acid in any proportion;
the curing agent is prepared through the following steps:
step S1, adding cystine and potassium hydroxide into absolute ethyl alcohol, stirring for 5min at 50 ℃, then heating to 55 ℃, adding vanillin, stirring for 30min, washing with diethyl ether after the reaction is finished, and recrystallizing with ethanol to obtain a Schiff base-containing intermediate;
s2, adding the Schiff base-containing intermediate and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide into tetrahydrofuran, heating and refluxing for reaction for 12 hours, and cooling and filtering after the reaction is finished to obtain the curing agent.
2. The epoxy resin corrosion-resistant floor paint of claim 1, wherein the epoxy resin is selected from one or more of bisphenol a epoxy resin, cycloaliphatic epoxy resin, bisphenol F epoxy resin, or phenolic epoxy resin.
3. The epoxy resin anti-corrosion floor paint according to claim 1, wherein the defoamer is one of 1340 defoamer, 822 defoamer and 805 defoamer; the dispersing agent is one of 602N dispersing agent and 5040 dispersing agent.
4. The epoxy resin anti-corrosion floor paint of claim 1, wherein the particle size of the modified filler is 400-600 mesh.
5. The method for preparing the epoxy resin anti-corrosion floor paint as claimed in claim 1, comprising the following steps:
firstly, mixing epoxy resin and deionized water according to parts by weight, stirring and dispersing for 30-40min to obtain a component A; mixing deionized water, a curing agent, a modified filler, a defoaming agent and a dispersing agent, and stirring and dispersing for 40-50min to obtain a component B;
and secondly, mixing the component A and the component B according to the mass ratio to obtain the epoxy resin anti-corrosion floor paint.
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| CN104745047B (en) * | 2015-04-22 | 2015-12-30 | 广东耐迪化工有限公司 | A kind of Self-leveling color mortar coatings material and preparation method thereof and constructional method |
| CN114249768A (en) * | 2020-09-24 | 2022-03-29 | 中国科学院宁波材料技术与工程研究所 | Phosphorus flame retardant based on amino acid and preparation method and application thereof |
| CN115160543A (en) * | 2022-08-11 | 2022-10-11 | 上海正欧实业有限公司 | Preparation method and application of environment-friendly flame-retardant amine curing agent |
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