Environment-friendly low-smoke fireproof coating and preparation method thereof
By using composite smoke inhibitors in fire-retardant coatings, including silica aerogel, nanoalumina and nanosilicon dioxide, the problem of the combustion of existing fire-retardant coatings generates a large amount of flue gas, achieving lower flue gas generation and better thermal insulation performance.
Patent Information
- Application Number
- CN202411976692.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-31
- Publication Date
- 2025-04-11
AI Technical Summary
The existing expansion fire-retardant coatings produce a large amount of toxic flue gas when burned, and the carbonization rate is low, resulting in a large amount of flue gas.
Compound smoke inhibitors, including silica aerogel, nano-alumina and nano-silica, are used to enhance the carbon-forming capacity of fire-retardant coatings through the high temperature stability of nano-alumina and the carbon layer formation ability of nano-silica, thereby reducing the generation of smoke.
It effectively reduces the amount of flue gas generated by the combustion of fire-resistant coatings, enhances the expansion ability of the carbon layer, maintains high crosslinking and improves thermal insulation performance.
Smart Images
Figure BDA0005220597060000011 
Figure FDA0005220597050000011
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of fire retardant coatings, and in particular to an environmentally friendly low-smoke fire retardant coating and a preparation method thereof. Background Art
[0002] Existing intumescent fire retardant coatings usually use resins and other polymers as film-forming agents, and are supplemented with carbonizing agents, carbonizing catalysts, foaming agents and inorganic fillers to achieve the purpose of flame retardancy and fire prevention. When the above-mentioned intumescent fire retardant coatings burn, a large amount of toxic and harmful gas smoke will be generated, seriously endangering the safety of nearby personnel.
[0003] The amount of smoke generated is closely related to the carbonization efficiency. The higher the carbonization rate, the less smoke is generated. However, the carbonization rate of existing intumescent fire retardant coatings is often low, resulting in a large amount of smoke generation.
[0004] The existing invention patent with application number 202211499659 discloses a water-based low-smoke fire retardant coating and a preparation method thereof. The fire retardant coating adds a ZnO / MoO3 / SiO2 aerogel composite smoke suppression material as a smoke suppressant to reduce the smoke generated by the combustion of the fire retardant coating. However, SiO2 aerogel will produce pore collapse under high temperature environment, resulting in reduced thermal insulation performance and promoting a decrease in carbonization effect. Summary of the invention
[0005] The purpose of the present invention is to solve the problems described in the above background technology. An environmentally friendly low-smoke fire-retardant coating and a preparation method thereof are proposed. The fire-retardant coating can reduce the smoke generated by combustion.
[0006] The technical solution adopted by the present invention to solve the technical problem is: an environmentally friendly low-smoke fire-retardant coating, which comprises the following components by mass:
[0007]
[0008] The composite smoke suppressant comprises the following components by weight:
[0009] 20-30 parts of silica aerogel,
[0010] 30-50 parts of nano-alumina,
[0011] 20-30 parts of nano silicon dioxide.
[0012] In the above technical scheme, the nano-alumina in the composite smoke suppressant has high temperature resistant inertness and high porosity, and has a certain smoke adsorption effect. The nano-alumina can adhere to the skeleton surface of the silica aerogel, thereby enhancing the high temperature resistance of the silica aerogel, so that the silica aerogel maintains a high stability in a high temperature environment. Nano-silica can promote the formation of a carbon layer, thereby reducing the generation of smoke.
[0013] Preferably, the compound resin is a mixture of epoxy resin and polyamide resin, and the mass ratio of the polyamide resin to the epoxy resin is 1:(1-3), and more preferably 1:1.2-1.4.
[0014] In the above technical scheme, the increase in the specific gravity of the epoxy resin is beneficial to enhancing the crosslinking degree of the polymer, thereby increasing the carbonization rate. However, the increase in the crosslinking degree increases the viscosity of the molten carbon layer, which is not conducive to the expansion of the carbon layer and the formation of a good carbon layer structure. The present invention introduces a composite smoke suppressant, through nano-silicon dioxide, silica aerogel and nano-alumina, to enhance the expansion capacity of the carbon layer while maintaining a high crosslinking degree.
[0015] Preferably, the intumescent flame retardant comprises the following components by mass:
[0016] 25-30 parts of ammonium polyphosphate,
[0017] 20-25 parts of melamine,
[0018] 20-30 parts of titanium dioxide,
[0019] 25-30 parts of oxidized cellulose.
[0020] Preferably, the oxidized cellulose is TEMPO oxidized cellulose nanofibers.
[0021] Preferably, the defoaming agent is selected from one or more of polyethylene glycol, polypropylene glycol, polyethylene oxide or polyether siloxane.
[0022] Preferably, the dispersant is selected from one or more of sodium tripolyphosphate, sodium hexametaphosphate or sodium pyrophosphate.
[0023] Preferably, the preparation method of the composite smoke suppressant comprises the following steps:
[0024] S1. Dissolve the formulated amount of silica aerogel in a sodium hydroxide solution, gradually add nano-alumina and stir continuously, and after the addition is complete, ultrasonically oscillate for 20-30 minutes to obtain an alumina-silica aerogel solution;
[0025] S2, adding nano-silica to the alumina-silica aerogel solution, and ultrasonically oscillating for 20-30 minutes to obtain an alumina-silica mixed solution;
[0026] S3, drying the alumina-silicon dioxide mixed solution at high temperature to obtain a composite smoke suppressant.
[0027] Preferably, the high temperature drying is: drying at 180-220° C. to constant weight.
[0028] A method for preparing the environmentally friendly low-smoke fire retardant coating as described above, the preparation method comprising the following steps:
[0029] S1, adding the formulated amount of intumescent flame retardant and dispersant to the diluent, stirring and mixing to obtain a first dispersion;
[0030] S2, adding the compounded resin and the composite smoke suppressant in the formula amount to the first dispersion, stirring and mixing, to obtain a second dispersion;
[0031] S3. Add the formulated amount of defoamer into the second dispersion, stir and mix well to obtain an environmentally friendly low-smoke fire retardant coating.
[0032] Preferably, in step S1, the stirring and mixing is specifically: a stirring rate of 400-600 rpm, a stirring time of 10-30 min, and more preferably a stirring rate of 500 rpm, and a stirring time of 15 min; in step S2, the stirring and mixing is specifically: a stirring rate of 500-700 rpm, a stirring time of 10-30 min, and more preferably a stirring rate of 600 rpm, and a stirring time of 15 min; in step S3, the stirring and mixing is specifically: a stirring rate of 600-800 rpm, a stirring time of 10-30 min, and more preferably a stirring rate of 700 rpm, and a stirring time of 15 min.
[0033] The beneficial effects of the present invention are:
[0034] 1. The present invention loads nano-alumina on the surface of the silica aerogel skeleton, so that the silica aerogel still has good stability at a higher temperature, and the fire retardant coating has good thermal insulation performance.
[0035] 2. The composite smoke suppressant of the present invention can enhance the charring ability of the fire retardant coating, thereby greatly reducing the generation of smoke.
[0036] 3. The present invention uses TEMPO oxidized cellulose nanofibers as a carbon source. The TEMPO oxidized cellulose nanofibers have high carboxyl groups, which can enhance the carbonization ability of the fire retardant coating and thereby reduce the generation of smoke. DETAILED DESCRIPTION
[0037] It should be noted that the following detailed descriptions are illustrative and are intended to provide further explanation of the present application. Unless otherwise specified, all technical and scientific terms used herein have the same meanings as those commonly understood by those skilled in the art to which the present application belongs.
[0038] It should be noted that the terms used herein are only for describing specific embodiments and are not intended to limit the exemplary embodiments according to the present application. As used herein, unless the context clearly indicates otherwise, the singular form is also intended to include the plural form. In addition, it should be understood that when the terms "comprise" and / or "include" are used in this specification, it indicates the presence of features, steps, operations, devices, components and / or combinations thereof.
[0039] The present invention is now further described in conjunction with specific examples. The following examples are only for explaining the present invention, but do not constitute a limitation of the present invention. The test samples and test processes used in the following examples include the following (if the specific experimental conditions are not indicated in the examples, they are usually in accordance with conventional conditions or the conditions recommended by the reagent company; the reagents, consumables, etc. used in the following examples, if not otherwise specified, can all be obtained from commercial channels).
[0040] Example 1
[0041] A method for preparing an environmentally friendly low-smoke fire-retardant coating, the steps of the preparation method are as follows:
[0042] S1. Add 50 parts of intumescent flame retardant and 6 parts of dispersant to 30 parts of diluent by mass, and stir at a rate of 500 rpm for 15 min to obtain a first dispersion;
[0043] S2. Add 30 parts of the composite resin and 10 parts of the composite smoke suppressant to the first dispersion, and stir at a rate of 600 rpm for 15 minutes to obtain a second dispersion;
[0044] S3. Add 3 parts of defoamer by mass to the second dispersion, and continue stirring at a rate of 700 rpm for 15 minutes to obtain an environmentally friendly low-smoke fire retardant coating.
[0045] The components of the intumescent flame retardant are as follows, by weight: 25 parts of ammonium polyphosphate, 20 parts of melamine, 20 parts of titanium dioxide and 25 parts of TEMPO oxidized cellulose nanofibers.
[0046] The compound resin is a mixture of epoxy resin and polyamide resin, the mass ratio of polyamide resin to epoxy resin is 1:1, the defoaming agent is polyether siloxane, and the dispersant is sodium tripolyphosphate.
[0047] The preparation method of the composite smoke suppressant comprises the following steps:
[0048] S1. Dissolve 25 parts of silica aerogel in sodium hydroxide solution by mass, gradually add 40 parts of nano-alumina and stir continuously, and after the addition is complete, ultrasonically vibrate for 20-30 minutes to obtain an alumina-silica aerogel solution;
[0049] S2, adding 25 parts of nano-silicon dioxide to the alumina-silicon dioxide aerogel solution, and ultrasonically oscillating for 20-30 minutes to obtain an alumina-silicon dioxide mixed solution;
[0050] S3. Dry the alumina-silicon dioxide mixed solution at 200° C. to a constant weight to obtain a composite smoke suppressant.
[0051] Example 2
[0052] The preparation method of the environmentally friendly low-smoke fire-retardant coating is the same as that in Example 1, except that the formula of the environmentally friendly low-smoke fire-retardant coating is as follows: 30 parts of compound resin, 20 parts of composite smoke suppressant, 50 parts of expanding flame retardant, 40 parts of diluent, 6 parts of dispersant, and 3 parts of defoaming agent.
[0053] Example 3
[0054] The preparation method of the environmentally friendly low-smoke fire-retardant coating is the same as that in Example 1, except that the formula of the environmentally friendly low-smoke fire-retardant coating is as follows: 30 parts of compound resin, 30 parts of composite smoke suppressant, 50 parts of expanding flame retardant, 40 parts of diluent, 6 parts of dispersant, and 3 parts of defoaming agent.
[0055] Example 4
[0056] The preparation method of the environmentally friendly low-smoke fire-retardant coating is the same as that in Example 1, except that the formula of the environmentally friendly low-smoke fire-retardant coating is as follows: 30 parts of compound resin, 10 parts of composite smoke suppressant, 55 parts of expanding flame retardant, 40 parts of diluent, 6 parts of dispersant, and 3 parts of defoaming agent.
[0057] Example 5
[0058] The preparation method of the environmentally friendly low-smoke fire-retardant coating is the same as that in Example 1, except that the formula of the environmentally friendly low-smoke fire-retardant coating is as follows: 30 parts of compound resin, 10 parts of composite smoke suppressant, 60 parts of expanding flame retardant, 40 parts of diluent, 6 parts of dispersant, and 3 parts of defoaming agent.
[0059] Example 6
[0060] The preparation method of the environmentally friendly low-smoke fire retardant coating is the same as that in Example 1, except that the mass ratio of the polyamide resin to the epoxy resin is 1:1.3.
[0061] Example 7
[0062] The preparation method of the environmentally friendly low-smoke fire retardant coating is the same as that in Example 1, except that the mass ratio of the polyamide resin to the epoxy resin is 1:2.
[0063] Example 8
[0064] The preparation method of the environmentally friendly low-smoke fire retardant coating is the same as that in Example 1, except that the mass ratio of the polyamide resin to the epoxy resin is 1:3.
[0065] Comparative Example 1
[0066] The preparation method of the environmentally friendly low-smoke fire retardant coating is the same as that of Example 1, except that the composite smoke suppressant does not contain nano-aluminum oxide.
[0067] Comparative Example 2
[0068] The preparation method of the environmentally friendly low-smoke fire retardant coating is the same as that of Example 1, except that the composite smoke suppressant does not contain nano-silicon dioxide.
[0069] Comparative Example 3
[0070] The preparation method of the environmentally friendly low-smoke fire retardant coating is the same as that of Example 1, except that the composite smoke suppressant does not contain silica aerogel.
[0071] Comparative Example 4
[0072] The preparation method of the environmentally friendly low-smoke fire retardant coating is the same as that of Example 1, except that the environmentally friendly low-smoke fire retardant coating formula does not contain a composite smoke suppressant.
[0073] Comparative Example 5
[0074] The preparation method of the environmentally friendly low-smoke fire-retardant coating is the same as that in Example 1, except that the environmentally friendly low-smoke fire-retardant coating formula does not contain a composite smoke suppressant, and the mass ratio of polyamide resin to epoxy resin is 1:1.3.
[0075] Comparative Example 6
[0076] The preparation method of the environmentally friendly low-smoke fire retardant coating is the same as that of Example 1, except that the environmentally friendly low-smoke fire retardant coating formula does not contain a composite smoke suppressant, and the mass ratio of polyamide resin to epoxy resin is 1:1.
[0077] Comparative Example 7
[0078] The preparation method of the environmentally friendly low-smoke fire retardant coating is the same as that of Example 1, except that the environmentally friendly low-smoke fire retardant coating formula does not contain a composite smoke suppressant, and the mass ratio of polyamide resin to epoxy resin is 1:1.5.
[0079] Comparative Example 8
[0080] The preparation method of the environmentally friendly low-smoke fire retardant coating is the same as that of Example 1, except that the formula of the environmentally friendly low-smoke fire retardant coating does not contain a composite smoke suppressant, and the mass ratio of polyamide resin to epoxy resin is 1:2.
[0081] According to GB / T 15442.2-1995 "Grading and test methods for fire retardant performance of decorative fire retardant coatings - large plate combustion method", the fire retardant performance of the environmentally friendly low-smoke fire retardant coatings prepared in Examples 1-8 and Comparative Examples 1-8 was tested.
[0082] According to GB / T 8627-2007 "Test method for smoke density of burning or decomposition of building materials", the smoke density of the environmentally friendly low-smoke fire retardant coatings prepared in Examples 1-8 and Comparative Examples 1-8 was tested.
[0083] The above test results are shown in Table 1.
[0084] Table 1
[0085] Flame retardant time (min) Maximum smoke density (%) Example 1 89 39 Example 2 95 33 Example 3 100 30 Example 4 98 42 Example 5 105 46 Example 6 96 30 Example 7 86 44 Example 8 73 51 Comparative Example 1 76 56 Comparative Example 2 82 54 Comparative Example 3 79 66 Comparative Example 4 73 73 Comparative Example 5 66 79 Comparative Example 6 63 82 Comparative Example 7 69 76 Comparative Example 8 68 82
[0086] From Table 1, it can be seen from Example 1, Example 2 and Example 3 that with the increase of the composite smoke suppressant in the fire retardant coating, the flame retardant time of the fire retardant coating gradually increases and the smoke density gradually decreases, indicating that the composite smoke suppressant can enhance the flame retardancy of the fire retardant coating and has a smoke suppression effect.
[0087] It can be seen from Example 1, Example 4 and Example 5 that with the increase of the intumescent flame retardant in the fire retardant coating, the flame retardant time of the fire retardant coating is significantly increased, but the smoke density also increases, indicating that the intumescent flame retardant generates smoke while enhancing the flame retardancy of the fire retardant coating.
[0088] It can be seen from Example 1, Example 6, Example 7 and Example 8 that as the mass ratio of polyamide resin to epoxy resin gradually decreases, the flame retardant time first increases and then decreases, and the smoke density also first decreases and then increases, indicating that as the specific gravity of the epoxy resin increases, the degree of cross-linking increases accordingly, but the expansion capacity of the charcoal layer weakens. When the two reach a balance, the flame retardancy and smoke suppression of the fire retardant coating reach the highest point.
[0089] From the comparison of Example 1, Comparative Example 1, Comparative Example 2 and Comparative Example 3, it can be seen that the fire retardant coating lacking nano-alumina, nano-silica or silica aerogel has a reduced flammability time and an increased smoke density, indicating that nano-alumina, nano-silica or silica aerogel can alone enhance the thermal insulation capacity of the fire retardant coating and reduce smoke generation.
[0090] In Comparative Example 4, the flame retardant time of the fire retardant coating without the composite smoke suppressant was significantly reduced, and the smoke density was significantly increased, indicating that the three have a synergistic effect, jointly promoting the formation of a dense carbon layer, enhancing thermal insulation performance and reducing smoke generation.
[0091] From the comparison between Example 5, Comparative Example 6 and Comparative Example 7, it can be seen that the mass ratio of polyamide resin to epoxy resin is optimal when it is 1:1.5, which indicates that the composite smoke suppressant can promote the expansion of the carbon layer while ensuring a high degree of cross-linking of the polymer.
[0092] In this specification, each embodiment is described in a progressive manner, and each embodiment focuses on the differences from other embodiments. The same or similar parts between the embodiments can be referred to each other. For the device disclosed in the embodiment, since it corresponds to the method disclosed in the embodiment, the description is relatively simple, and the relevant parts can be referred to the method part.
[0093] The above is a detailed introduction to an environmentally friendly low-smoke fire retardant coating and a preparation method thereof provided by the present invention. This article uses specific examples to illustrate the principles and implementation methods of the present invention. The description of the above embodiments is only used to help understand the method of the present invention and its core idea. It should be pointed out that for ordinary technicians in this technical field, without departing from the principles of the present invention, the present invention can also be improved and modified in a number of ways, and these improvements and modifications also fall within the scope of protection of the claims of the present invention.
Claims
1. An environmentally friendly low-smoke fire retardant coating, characterized in that: The environmentally friendly low-smoke fire retardant coating comprises the following components by mass: The composite smoke suppressant comprises the following components by weight: 20-30 parts of silica aerogel, 30-50 parts of nano-alumina, 20-30 parts of nano silicon dioxide.
2. The environmentally friendly low-smoke fire retardant coating according to claim 1, characterized in that: The compound resin is a mixture of epoxy resin and polyamide resin, and the mass ratio of the polyamide resin to the epoxy resin is 1:(1-3).
3. The environmentally friendly low-smoke fire retardant coating according to claim 1, characterized in that: The intumescent flame retardant comprises the following components by mass: 25-30 parts of ammonium polyphosphate, 20-25 parts of melamine, 20-30 parts of titanium dioxide, 25-30 parts of oxidized cellulose.
4. The environmentally friendly low-smoke fire retardant coating according to claim 3 is characterized in that: The oxidized cellulose is TEMPO oxidized cellulose nanofibers.
5. The environmentally friendly low-smoke fire retardant coating according to claim 1, characterized in that: The defoaming agent is selected from one or more of polyethylene glycol, polypropylene glycol, polyethylene oxide alcohol or polyether siloxane.
6. The environmentally friendly low-smoke fire retardant coating according to claim 1, characterized in that: The dispersant is selected from one or more of sodium tripolyphosphate, sodium hexametaphosphate or sodium pyrophosphate.
7. The environmentally friendly low-smoke fire retardant coating according to claim 1, characterized in that: The preparation method of the composite smoke suppressant comprises the following steps: S1. Dissolve the formulated amount of silica aerogel in a sodium hydroxide solution, gradually add nano-alumina and stir continuously, and after the addition is complete, ultrasonically oscillate for 20-30 minutes to obtain an alumina-silica aerogel solution; S2, adding nano-silica to the alumina-silica aerogel solution, and ultrasonically oscillating for 20-30 minutes to obtain an alumina-silica mixed solution; S3, drying the alumina-silicon dioxide mixed solution at high temperature to obtain a composite smoke suppressant.
8. The environmentally friendly low-smoke fire retardant coating according to claim 7, characterized in that: The high temperature drying specifically includes: drying at 180-220° C. to constant weight.
9. A method for preparing the environmentally friendly low-smoke fire retardant coating according to any one of claims 1 to 8, characterized in that: The preparation method comprises the following steps: S1, adding the formulated amount of intumescent flame retardant and dispersant to the diluent, stirring and mixing to obtain a first dispersion; S2, adding the compounded resin and the composite smoke suppressant in the formula amount to the first dispersion, stirring and mixing, to obtain a second dispersion; S3. Add the formulated amount of defoamer into the second dispersion, stir and mix well to obtain an environmentally friendly low-smoke fire retardant coating.
10. The environmentally friendly low-smoke fire retardant coating according to claim 9, characterized in that: In step S1, the stirring and mixing is specifically: stirring rate 400-600rpm, stirring time 10-30min; in step S2, the stirring and mixing is specifically: stirring rate 500-700rpm, stirring time 10-30min; in step S3, the stirring and mixing is specifically: stirring rate 600-800rpm, stirring time 10-30min.