CN113731778B - Surface construction method of green inorganic fireproof paint - Google Patents

Surface construction method of green inorganic fireproof paint Download PDF

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Publication number
CN113731778B
CN113731778B CN202010414253.9A CN202010414253A CN113731778B CN 113731778 B CN113731778 B CN 113731778B CN 202010414253 A CN202010414253 A CN 202010414253A CN 113731778 B CN113731778 B CN 113731778B
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sodium alginate
inorganic
coating
construction method
substrate
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CN113731778A (en
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张尚权
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Guangdong Guangna New Material Co ltd
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Guangdong Guangna New Material Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/54—No clear coat specified
    • 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
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • 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
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • 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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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Building Environments (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention discloses a surface construction method of a green inorganic fireproof coating. The fireproof paint is an inorganic flame-retardant material taking a silicon-based material as a main body, the cross-linked material is sodium alginate and other organic matters, the construction method is brushing or spraying layer by layer, and the green rapid construction and tight combination of the inorganic flame-retardant material on different substrates are realized by utilizing the reverse spheroidization of the silicon-based material adsorbed with calcium ion solution as an initiator and the sodium alginate. The invention has the advantages of easily available raw materials, simple and convenient process, environmental protection, effective crosslinking of the inorganic silicon material rich in metal ions and sodium alginate, formation of the outer sodium alginate, reverse spheroidization coating of the shell and core of the inorganic silicon, reinforcement of the combination degree of the inorganic fireproof coating and the substrate, and reduction of the possibility of stripping or inactivation.

Description

Surface construction method of green inorganic fireproof paint
Technical Field
The invention relates to the technical field of inorganic fireproof paint construction, in particular to a construction method of inorganic fireproof paint on different substrates.
Background
With the rapid development of modern society, the requirements for fire protection are increasing. The main stream fireproof materials in the current market mainly comprise organic fireproof coatings of bromine series, phosphorus and nitrogen series, red phosphorus and compounds, and the organic fireproof materials can be closely adhered to different base materials through adhesion with a high polymer adhesive, so that the main stream fireproof materials have great advantages for construction and long-term storage of the fireproof coatings. However, the fireproof paint is inflammable, has short flame-retardant time, can generate a large amount of toxic and harmful gases such as organic volatile matters (VOCs) and the like in the flame-retardant process, and can seriously endanger the life safety of personnel. There is therefore a very urgent market need to develop another green inorganic fire retardant coating. In recent years, silicon-based fireproof paint represented by silicon dioxide aerogel has larger advantages in heat conductivity coefficient, flame retardant time, release of combustion pollutants and the like compared with organic flame retardant materials, so that the silicon-based fireproof paint has great application prospects in the fields of new energy electric automobile batteries, building households, special fire protection, aerospace and the like. However, because the structural brittleness and the assembly capability of the inorganic matters are greatly different from those of the organic materials, serious problems such as powder falling, stripping, moisture absorption, deterioration and the like often occur in the construction process and the subsequent protection process of the inorganic fireproof coating, and the service efficiency and the service life of the inorganic fireproof coating are seriously influenced. The conventional solution is to adhere the inorganic coating materials with an organic binder, but the toxic and harmful substances such as formaldehyde and fluorine-containing organic substances which are rich in the inorganic coating materials still generate a large amount of toxic and harmful gases in the combustion process. Meanwhile, the compatibility of the binders and inorganic coatings is poor, and uniform and effective dispersion and optimal fireproof flame retardant performance cannot be achieved in the construction process.
Disclosure of Invention
In view of the above, the present invention discloses a construction method of inorganic fireproof paint, which is mainly aimed at the surface construction scheme of silicon-based inorganic fireproof paint on different substrates.
The invention provides a surface construction method of an inorganic fireproof coating, which comprises the following preparation steps:
(a) And cleaning the surface of the substrate by using clear water and an organic solvent respectively to remove surface pollutants. Preparing a sodium alginate solution with a certain concentration and a specific ph, and spraying or brushing the sodium alginate solution on the surface of a substrate to uniformly load and fix a certain amount of sodium alginate on the surface of the substrate;
(b) Dispersing proper porous inorganic fireproof material in metal ion solution with certain concentration, and dispersing to make the metal ion adsorbed on the inorganic fireproof material homogeneously;
(c) Brushing or spraying the solution which is uniformly mixed and dispersed on a sodium alginate loaded substrate to enable the sodium alginate and the material to carry out a cross-linking reaction of reverse spheroidization, thereby achieving the purpose of fixing the inorganic fireproof material in the sodium alginate;
(d) The crosslinked inorganic fireproof material coating is subjected to proper compaction treatment, and the coating is further cured. Preferably, in the step (a), the stabilizer is chitosan, sodium alginate or hydroxypropyl methylcellulose.
Further, in the step (a), ph of the sodium alginate solution is 8-14.
Preferably, in the step (a), the preparing solution is water, and the mass ratio of the water to the sodium alginate is 1: (0.05-0.002).
Preferably, in the step (a), a thickener such as sodium carboxymethyl cellulose or sodium polyacrylate and the like can be added for different substrates to increase the degree of compounding, and the mass ratio of the thickener to sodium alginate is 1 (100-1000).
Preferably, in the step (b), the inorganic fireproof coating is prepared by using SiO 2 Typically an active or porous silicon-based material, having a specific surface area>50m 2 /g。
Preferably, in the step (b), the solvent for dispersing the inorganic fireproof paint may adjust a mixed solution of water and alcohol such as absolute ethanol according to the hydrophilicity and the volume ratio of the alcohol to the water is 1: (1-100), the mass ratio of the inorganic fireproof coating to the solution is 1 (0.001-1).
Preferably, in the step (b), the inorganic fireproof coating may be dispersed by stirring and ultrasonic waves for 10 to 30 minutes.
Preferably, in the step (b), the metal ion is one or more of alkali or transition metal ions such as Na, ca, cu, etc., and the concentration of the metal ion solution is 0.1-100 g/L.
Furthermore, in the step (c), the inorganic fireproof coating mixed solution adsorbing the metal ions can be loaded on the sodium alginate coating in a brushing or spraying mode, water is sprayed to perform activation crosslinking in the construction process, 3 times of brushing or spraying of inorganic coatings are ensured, 1 time of spraying water participates in crosslinking reaction, and the spraying amount of 1 time of water is consistent with the spraying amount of 1 time of inorganic solution. The ratio of the solution amount of the spraying inorganic coating to the construction area is (1-200 ml): 1m 2 。
Preferably, in the step (d), the crosslinking reaction time is 0.2 to 1h.
Preferably, in the step (d), a certain pressure is applied by using a pressing plate after the crosslinking is completed, so as to promote the contact degree of the crosslinked coating and the substrate, and the applied pressure is 500-2000 Pa.
The invention also discloses a green electrodeless fireproof coating, which is obtained by the surface construction method and comprises a cross-linked sodium alginate as an outer shell and a reverse spheroidized core-shell structure layer of a silicon-based material as an inner layer, wherein the core-shell structure layer is obtained by the cross-linking reaction of metal ions adsorbed on the surface of the silicon-based fireproof material and sodium alginate tightly compounded on a substrate.
The construction schematic diagram of the inorganic fireproof coating disclosed by the invention is shown in fig. 1.
The adhesive used in the surface construction method of the inorganic coating is an aqueous inorganic polymer mainly containing sodium alginate, has the characteristics of green and environment-friendly properties, strong adhesion and the like, and can achieve the purpose of crosslinking and adhering on different base material plates only by a small amount of addition. The silicon-based inorganic paint has better adsorption effect on metal ions, so that each inorganic paint unit is uniformly loaded with a certain amount of metal ions. The principle of construction crosslinking is to utilize the phenomenon of reverse spheroidization in the crosslinking process of sodium alginate and metal. The method comprises the steps of immersing a carrier containing low concentration metal ions into sodium alginate with high concentration, carrying out cross-linking colloid to form an outer coated sodium alginate, wherein the inner layer is a shell-core structure of an inorganic coating containing metal ions.
Compared with the prior art, the invention has the advantages that the raw materials are easy to obtain, the process is simple and convenient, the industrial production is facilitated, the adopted inorganic coating construction technology can be loaded on the surfaces of different substrates by adjusting the content of sodium alginate and metal ions and the ph value, and the invention has better universality. Meanwhile, the synthesized outer layer is sodium alginate, the inner layer is a coating of an inorganic fireproof coating structure, the coating can be closely loaded on different substrates, the possibility of powder falling, peeling, wetting, deterioration and the like does not exist, other toxic and harmful substances can not exist during combustion, and the flame retardant effect is not influenced.
Drawings
FIG. 1 is a schematic view of the construction of the inorganic flame retardant coating disclosed by the invention.
FIG. 2 is a Scanning Electron Microscope (SEM) morphology of the front surface of the inorganic flame retardant material after surface construction in example 1.
FIGS. 3 and 4 are a morphology view and an enlarged view of a side face of the inorganic flame retardant material after surface construction in example 1.
Fig. 5 and 6 are a morphology view and an enlarged view of a scanning electron microscope on a side surface of the inorganic flame retardant material subjected to surface construction in example 1 after being burned at a high temperature.
FIG. 7 is a thermogravimetric analysis change plot of the electrodeless flame retardant coating of example 1.
Detailed Description
The following examples are further illustrative of the technical content of the present invention, but the essential content of the present invention is not limited to the examples described below, and those skilled in the art can and should know that any simple changes or substitutions based on the essential spirit of the present invention should fall within the scope of the present invention as claimed.
The test materials, reagents and the like used in the examples described below are commercially available unless otherwise specified, and those not specifically mentioned in the examples may be carried out according to the techniques or conditions described in the literature in the field or according to the specifications of the products.
The invention provides a surface construction method of inorganic fireproof paint, which is characterized in that the construction steps comprise the following steps:
a) And cleaning the surface of the substrate by using clear water and an organic solvent respectively to remove surface pollutants. Preparing a sodium alginate solution with a certain concentration and a specific ph, and spraying or brushing the sodium alginate solution on the surface of a substrate to uniformly load and fix a certain amount of sodium alginate on the surface of the substrate;
(b) Dispersing proper porous inorganic fireproof material in metal ion solution with certain concentration, and dispersing to make the metal ion adsorbed on the inorganic fireproof material homogeneously;
(c) Brushing or spraying the solution which is uniformly mixed and dispersed on a sodium alginate loaded substrate to enable the sodium alginate and the material to carry out a cross-linking reaction of reverse spheroidization, thereby achieving the purpose of fixing the inorganic fireproof material in the sodium alginate;
(d) The crosslinked inorganic fireproof material coating is subjected to proper compaction treatment, and the coating is further cured.
Example 1
Example 1 provides a construction method of inorganic fireproof paint on the surface of organic plastic, which comprises the following detailed preparation steps:
1g of sodium alginate is dissolved in 20ml of deionized water in a beaker, pH is adjusted to 11 by ammonia water, and then 5g of SiO is weighed by taking the beaker 2 Hydrophilic aerogel is dispersed in 5mL deionized water, after ultrasonic dispersion is carried out for 30 minutes, 2g of calcium chloride is added into the solution for adsorption treatment, and after stirring and adsorption are carried out for 30 minutes. Firstly, sodium alginate solution is sprayed on an organic plastic substrate (the area is 5m 2 ) On the surface, and air-dried and left to stand for 30 minutes. And then SiO which adsorbs calcium ions 2 Spraying the aerogel mixed solution on an organic plastic substrate loaded with sodium alginate for 3 times, and then spraying deionized water for 1 time to accelerate the crosslinking reaction. And air-drying and standing for 30 minutes after the spraying is finished, and compacting the crosslinked pellets with the substrate by applying 1000Pa force by using a pressing plate.
The particle size of the pellets yielding the core-shell structure was found to be on average 500nm by transmission electron microscopy. 180 degree horizontal peel strength was 150N/cm.
Fig. 2 is a morphology of the inorganic flame retardant material of example 1 after surface construction, which is tightly adhered to the surface of the substrate in the form of small spherical particles.
Fig. 3 and 4 are side views of the inorganic flame retardant material after surface construction in example 1, and the thickness thereof is 300 μm or more. From fig. 3, it can be seen that a large amount of sodium alginate high molecular polymer encapsulates the inorganic flame retardant material.
Fig. 5 and 6 are side views of the inorganic flame retardant material of example 1 after being burned at high temperature, wherein the inorganic flame retardant material has a volume which is significantly expanded and is in a porous state.
FIG. 7 is a thermogravimetric analysis of the inorganic flame retardant coating of example 1, from which it can be seen that a severe endothermic reaction occurs around 100-200 degrees and rapidly decomposes and expands thereafter, providing flame retardant and thermal insulation effects.
Example 2
Example 2 provides a construction method of inorganic fireproof paint on a metal surface, and the detailed preparation steps are as follows:
1g of sodium alginate was dissolved in 20ml of deionized water in a beaker, ph was adjusted to 14 by ammonia water, and then 5g of SiO was weighed into the beaker 2 Hydrophilic aerogel is dispersed in 5mL deionized water, after ultrasonic dispersion is carried out for 30 minutes, 4g of calcium chloride is added into the solution for adsorption treatment, and after stirring and adsorption are carried out for 30 minutes. Firstly, sodium alginate solution is sprayed on an organic plastic substrate (the area is 5m 2 ) On the surface, and air-dried and left to stand for 30 minutes. And then SiO which adsorbs calcium ions 2 Spraying the aerogel mixed solution on an organic plastic substrate loaded with sodium alginate for 3 times, and then spraying deionized water for 1 time to accelerate the crosslinking reaction. And air-drying and standing for 30 minutes after the spraying is finished, and compacting the crosslinked pellets with the substrate by applying 1000Pa force by using a pressing plate.
The particle size of the pellets yielding the core-shell structure was found to be 100nm on average by transmission electron microscopy. 180 degree horizontal peel strength was 100N/cm.
Example 3
Example 3 provides a construction method of inorganic fireproof paint on the surface of wood, and the detailed preparation steps are as follows:
1g of sodium alginate is dissolved in 20ml of deionized water in a beaker, pH is adjusted to 9 by ammonia water, and then 5g of SiO is weighed by taking the beaker 2 Hydrophilic aerogel is dispersed in 5mL deionized water, after ultrasonic dispersion is carried out for 30 minutes, 1g of calcium chloride is added into the solution for adsorption treatment, and after stirring and adsorption are carried out for 30 minutes. Firstly, sodium alginate solution is sprayed on an organic plastic substrate (area5m 2 ) On the surface, and air-dried and left to stand for 30 minutes. And then SiO which adsorbs calcium ions 2 Spraying the aerogel mixed solution on an organic plastic substrate loaded with sodium alginate for 3 times, and then spraying deionized water for 1 time to accelerate the crosslinking reaction. And air-drying and standing for 30 minutes after the spraying is finished, and compacting the crosslinked pellets with the substrate by applying 500Pa force by using a pressing plate.
The particle size of the pellets yielding the core-shell structure was measured by transmission electron microscopy at an average of 1000nm.180 degree horizontal peel strength was 200N/cm.
Example 4
Example 4 provides a construction method of inorganic fireproof paint on the surface of packaging paper, and the detailed preparation steps are as follows:
1g of sodium alginate was dissolved in 5ml of deionized water in a beaker, ph was adjusted to 8 by ammonia water, and then 1g of SiO was weighed into the beaker 2 Hydrophilic aerogel is dispersed in 2mL deionized water, after ultrasonic dispersion is carried out for 30 minutes, 0.5g copper chloride is added into the solution for adsorption treatment, and after stirring and adsorption are carried out for 30 minutes. Firstly, sodium alginate solution is sprayed on an organic plastic substrate (the area is 5m 2 ) On the surface, and air-dried and left to stand for 30 minutes. And then SiO which adsorbs calcium ions 2 Spraying the aerogel mixed solution on an organic plastic substrate loaded with sodium alginate for 3 times, and then spraying deionized water for 1 time to accelerate the crosslinking reaction. And air-drying and standing for 30 minutes after the spraying is finished, and compacting the crosslinked pellets with the substrate by applying 500Pa force by using a pressing plate.
The particle size of the pellets yielding the core-shell structure was measured by transmission electron microscopy at an average of 400nm.180 degree horizontal peel strength was 180N/cm.
Comparative example 1
And directly spraying the silicon dioxide aerogel on the organic plastic substrate without adding sodium alginate.
The silica aerogel is measured by a scanning electron microscope to be in blocky agglomeration distribution, the substrate is unevenly distributed, and a large amount of blank exists. 180 degree horizontal peel strength was 30N/cm.
Table 1 comparison of Critical parameters such as surface Peel force, thermal conductivity before and after burning, volume expansion Rate of inorganic flame retardant coating in examples
As can be seen from the experimental results of the above examples and comparative examples, the surface construction method of the inorganic fireproof coating disclosed by the invention has strong adhesive force to different substrates, can uniformly disperse the inorganic fireproof coating, and has universality.

Claims (9)

1. The surface construction method of the green inorganic fireproof paint is characterized by comprising the following steps of:
(a) Cleaning the surface of a substrate by using clear water and an organic solvent respectively, removing surface pollutants, preparing sodium alginate solution, and spraying or brushing the sodium alginate solution on the surface of the substrate to uniformly load and fix the sodium alginate on the surface of the substrate;
(b) Dispersing inorganic porous fireproof material in metal ion solution, and dispersing to make metal ion be adsorbed on inorganic fireproof material uniformly to form uniformly dispersed mixed slurry;
(c) Brushing or spraying the uniformly dispersed mixed slurry on a sodium alginate loaded substrate to enable the sodium alginate and the mixed slurry to carry out a cross-linking reaction of 'reverse spheroidization', and fixing the inorganic fireproof material in the sodium alginate;
(d) Compacting the crosslinked inorganic fireproof material coating, and further curing the coating;
the mass ratio of water in sodium alginate to sodium alginate is 1: (0.05-0.002);
the dispersion concentration of the metal ion solution is 0.1-100 g/L.
2. The construction method according to claim 1, wherein in the step (a), the pH of the sodium alginate solution is 8 to 14, and the liquid is water.
3. The construction method according to claim 1, wherein the substrate is metal, the sodium alginate solution further contains aqueous sodium carboxymethylcellulose (CMC) and/or sodium polyacrylate thickener, and the mass ratio of the thickener to sodium alginate is 1: (100-1000).
4. The construction method according to claim 1, wherein in the step (b), the inorganic porous fireproof material is silica aerogel having a specific surface area>50m 2 And/g, dispersing the inorganic porous fireproof material in the mixed slurry by using a mixed solvent of water and an organic solvent, wherein the organic solvent is ethanol, the volume ratio of ethanol to water is 1 (1-100), and the mass ratio of the inorganic porous fireproof coating to the solvent is 1 (0.001-1).
5. The method according to claim 1, wherein in the step (b), the metal ion solution is one or more of alkali metal ions such as Na, ca, cu, and the like, or transition metal ions.
6. The construction method according to claim 1, wherein the dispersion treatment in the step (b) is a dispersion treatment using ultrasound and/or stirring for 10 to 30 minutes.
7. The construction method according to claim 1, wherein in the step (c), the uniformly dispersed mixed slurry is loaded on the sodium alginate coating in a spray coating or brush coating manner, and in the construction process, the supply of deionized water is ensured, so that the crosslinking reaction of the metal ions of the reverse spheroidization and the sodium alginate is continuously performed, thereby finally coating the inorganic silicon material to form a core-shell structure, and the ratio of the amount of the mixed slurry to the construction area is (1-200 ml): 1m 2 。
8. The method according to claim 1, wherein in the step (d), the crosslinking reaction time is 0.2 to 1h, and after the crosslinking reaction is completed, a pressure of 500 to 2000Pa is applied to the coating layer, so that the degree of contact between the coating layer and the substrate after the crosslinking is enhanced.
9. The green inorganic fireproof coating obtained by the surface construction method according to any one of claims 1 to 8, which is characterized by comprising a cross-linked sodium alginate as an outer shell and a reverse spheroidized core-shell structure layer of a silicon-based fireproof material as an inner layer, wherein the core-shell structure layer is obtained by cross-linking reaction of metal ions adsorbed on the surface of the silicon-based fireproof material and sodium alginate tightly compounded on a substrate.
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