CN111548663A - Preparation method of intumescent flame-retardant coating - Google Patents
Preparation method of intumescent flame-retardant coating Download PDFInfo
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Abstract
The invention discloses a preparation method of an intumescent flame retardant coating, which relates to the field of coating preparation and comprises the following preparation steps: 1) heating polyvinyl alcohol until the polyvinyl alcohol is stirred and dissolved, then adding glycerol, linseed oil, acetaldehyde and an emulsifier, keeping the temperature, stirring, then cooling, adding vermiculite, soaking, and drying to obtain oil film coated vermiculite; 2) mixing polyoxytetramethylene glycol and hexamethylene diisocyanate for reaction, adding trimethylolpropane for reaction, adding hydroxypropyl methacrylate for heat preservation reaction, and adding triethylamine for neutralization to prepare a prepolymer; 3) adding water into the prepolymer, stirring, and adding azodiisobutyronitrile and hydroxypropyl methacrylate to prepare a polyurethane acrylate emulsion; 4) the intumescent flame retardant coating is prepared by adding an oil film to coat vermiculite into a polyurethane acrylate emulsion, and the intumescent flame retardant coating prepared by the invention has the advantages of good expansibility, high fireproof performance, high strength, good water and alkali resistance, simple preparation method and suitability for industrial use.
Description
Technical Field
The invention relates to the field of paint preparation, in particular to a preparation method of an intumescent flame retardant paint.
Background
With the rapid development of economic society and the abundance of the living standard of people, the floors of the commercial new houses are higher and higher. Large population aggregates are building facilities are increasing and are also demanding aesthetically. At present, with the more serious economic and safety consequences caused by fire, people have higher and higher requirements on flame retardance of building coatings. At present, most of coatings in the prior art are flame-retardant coatings containing halogen flame retardants, which are favored by numerous coating manufacturers due to the stable properties and high flame-retardant efficiency of the halogen flame retardants, but the halogen flame retardants can generate smoke during combustion and are mixed with a large amount of solid particles, and the halogen-containing flame-retardant coatings can release toxic gas during combustion, but have high air pollution and can influence the breathing of people, so that people are suffocated and poisoned when fires happen.
For example, a Chinese patent document discloses "a waterborne polyurethane flame retardant coating and a preparation method", and publication No. CN109337421A discloses a waterborne polyurethane flame retardant coating and a preparation method. The preparation method comprises the following preparation processes: (1) melting antimony at the temperature of 1000-1300 ℃ under the air pressure of 1MPa, colliding with micron-sized wollastonite powder by high-pressure airflow, and depositing antimony trioxide superfine particles on the surfaces of the particles to prepare the composite particle material with a core-shell structure; (2) compounding with decabromodiphenylethane to prepare a halogen-antimony system synergistic flame retardant; (3) mixing pentaerythritol triacrylate, high chlorinated polyethylene resin, polyurethane resin and methyl silicone resin, and adding into deionized water to obtain a mixed solution; (4) and adding a film-forming auxiliary agent, a thickening agent, a flatting agent, a dispersing agent, a defoaming agent and a synergistic flame retardant into the mixed solution, and stirring and grinding to obtain the water-based flame-retardant coating. However, the brominated flame retardant decabromodiphenylethane used in the flame retardant coating can generate polluted smoke during combustion, is mixed with a large amount of solid particles, and can release toxic gas, so that the flame retardant coating has great air pollution, influences the breathing of people and causes suffocation poisoning of people during fire.
Disclosure of Invention
The invention provides a preparation method of an intumescent flame retardant coating, aiming at overcoming the problems that most of the existing coatings in the prior art are flame retardant coatings containing halogen flame retardants, during the combustion process, the halogen flame retardants can generate polluted smog during the combustion, and are mixed with a large amount of solid particles, and the halogen flame retardant coatings can release toxic gases during the combustion, so that the pollution to air is large, the breathing of people can be influenced, and the suffocation and poisoning of people during the fire disaster can be caused.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of an intumescent flame retardant coating comprises the following preparation steps:
(1) heating 30-50 parts of polyvinyl alcohol to 80-90 ℃, stirring for dissolving, then adding 2-5 parts of glycerol, 3-9 parts of linseed oil, 0.5-1 part of acetaldehyde and 0.5-1 part of emulsifier, keeping the temperature, stirring for 0.5-1.5h, then cooling to 25-35 ℃, adding 10-15 parts of vermiculite, soaking for 2-4h, taking out and drying to obtain oil film coated vermiculite;
(2) mixing 50-60 parts of polyoxytetramethylene glycol and 15-20 parts of hexamethylene diisocyanate at 65-85 ℃ for reaction for 2.5-6h, then adding 1.5-3 parts of trimethylolpropane at 80-90 ℃ for reaction for 4-7h, then adding 10-15 parts of hydroxypropyl methacrylate for heat preservation reaction for 1-2h, and adding 1-3 parts of triethylamine after the reaction is finished for neutralization to prepare a prepolymer;
(3) adding water into the prepolymer, stirring for 1-1.5h, and then adding 0.5-1 part of azodiisobutyronitrile and 5-8 parts of hydroxypropyl methacrylate to prepare a polyurethane acrylate emulsion;
(4) and adding an oil film to coat vermiculite into the polyurethane acrylate emulsion to prepare the intumescent flame retardant coating.
When the flame-retardant coating is prepared, the waterborne polyurethane acrylate emulsion is prepared firstly, water is used as a dispersion medium for the waterborne polyurethane acrylate emulsion instead of an organic solvent, the VOC emission is low, the coating is safe and environment-friendly, the waterborne polyurethane acrylate paint film also has excellent mechanical property, wear resistance, aging resistance, water resistance and alkali resistance, and then vermiculite is added into the waterborne polyurethane emulsion, is of a layered structure, and rapidly expands in volume at high temperature, so that the excellent heat insulation and fire resistance are achieved. The vermiculite is characterized in that a large amount of crystal water is arranged between vermiculite layers, and water vapor between the layers evaporates in the heating process to form strong steam pressure between the layers, so that the interlayer distances are separated, and the volume is expanded.
Preferably, the polymerization degree of the polyvinyl alcohol in the step (1) is 1700; the alcoholysis degree is 98-99%.
The polyvinyl alcohol adopted by the invention has higher polymerization degree and alcoholysis degree, and prevents an oil film coated by vermiculite from dissolving in the water-based emulsion.
Preferably, the emulsifier in step (1) comprises one or more of tween 20, tween 60 and tween 80.
Preferably, the solid content of the polyurethane acrylate emulsion in step (3) is 40 to 50 wt%.
Preferably, 10-15 wt% of oil film coated vermiculite is added in the step (4).
Preferably, the oil film coated vermiculite is modified by gel coating, and comprises the following steps:
a: putting hydroxymethyl cellulose into water to prepare a 2-4% hydroxymethyl cellulose aqueous solution;
b: putting the oil film coated vermiculite into a hydroxymethyl cellulose aqueous solution, uniformly stirring to obtain a mixed solution, and then dripping the mixed solution into a coagulating bath to prepare wet gel;
c: and (3) carrying out solvent replacement, freeze drying and grinding on the wet gel to prepare the oil film coated vermiculite cellulose gel.
In experiments, the oil film coated vermiculite is found to have poor dispersibility in emulsion, so that the coating is prone to uneven expansion when encountering fire and cannot achieve the purpose of excellent heat insulation protection, the oil film coated vermiculite is easy to separate out from the coating, the fireproof effect of the material is affected, and the overall strength of the coating is low. After the oil film coated vermiculite is added into the filler in a gel coating mode, the oil film coated vermiculite has better dispersibility in water, and the phenomenon of uneven expansion is prevented.
Preferably, the mass ratio of the oil film coated vermiculite to the hydroxymethyl cellulose is 1: 1.5-2.
Preferably, the oil film coated vermiculite cellulose gel is subjected to expansion modification: putting hexamethylene diisocyanate into toluene, and dropwise adding monolauryl phosphate to react for 4-7h at 65-75 ℃ under the protection of nitrogen to prepare an intermediate product reaction liquid; and placing the oil film coated vermiculite cellulose gel into an intermediate product reaction solution, continuously reacting for 4-7h at 65-75 ℃ under the protection of nitrogen, washing, and then carrying out vacuum freeze drying to prepare the expansion modified oil film coated vermiculite cellulose gel.
According to the invention, the oil film-coated vermiculite cellulose gel is subjected to expansion modification, so that the oil film-coated vermiculite cellulose gel is endowed with further expansion performance. Through expansion modification, nitrogen and phosphorus are successfully introduced into the oil film-coated vermiculite cellulose gel, so that the flame retardant property of the oil film-coated vermiculite cellulose gel is improved, metaphosphoric acid is firstly generated when the oil film-coated vermiculite cellulose gel meets fire, dehydration and carbonization of cellulose are promoted, then, due to the existence of the nitrogen, nitric oxide, nitrogen dioxide and other gases can be generated after the oil film-coated vermiculite cellulose gel meets fire, and small gas molecules can dilute oxygen in air to play a role in flame retardance on one hand, and can play a role in promoting expansion and foaming of carbonized cellulose and oil film-coated vermiculite on the other hand, so that a better heat source isolation effect is achieved, and the fireproof property of the coating is further improved.
Preferably, the mole ratio of the hexamethylene diisocyanate to the monolauryl phosphate is 2-5: 1.
In the preparation of the intermediate product, the molar amount of hexamethylene diisocyanate is greater than that of monolauryl phosphate, so that monolauryl phosphate reacts more with one of the terminal isocyanate groups of hexamethylene diisocyanate, and the other terminal isocyanate group is used for bonding with the oil film-coated vermiculite cellulose gel, so that the intermediate product can be fixed in the gel.
Preferably, the mass ratio of the oil film-coated vermiculite cellulose gel to the hexamethylene diisocyanate is 1: 1-1.3.
Therefore, the invention has the following beneficial effects:
(1) the addition of vermiculite increases the heat insulation and fire resistance of the coating, and simultaneously, the vermiculite is coated with an oil film, so that the expansion volume of the vermiculite is increased, and the heat insulation and fire resistance are improved;
(2) according to the invention, oil film coated vermiculite is modified by gel coating and added into the coating in a form of oil film coated vermiculite cellulose gel, so that the dispersibility of the oil film coated vermiculite is enhanced, the oil film coated vermiculite is prevented from being separated out, and the strength of the coating is increased;
(3) through further expansion modification of oil film coated vermiculite cellulose gel, the oil film coated vermiculite cellulose gel is endowed with better flame retardance and fire expansion performance, and the fireproof effect is improved;
(4) the coating prepared by the invention is safe and environment-friendly, has high strength and good water and alkali resistance, and the preparation method is simple and is suitable for industrial use.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1: a preparation method of an intumescent flame retardant coating comprises the following preparation steps:
(1) heating 40 parts of polyvinyl alcohol to 85 ℃, stirring and dissolving, then adding 3 parts of glycerol, 6 parts of linseed oil, 0.8 part of acetaldehyde and 0.7 part of tween 80, keeping the temperature and stirring for 1 hour, then cooling to 30 ℃, adding 13 parts of vermiculite, soaking for 3 hours, taking out and drying to obtain oil film coated vermiculite; wherein the polymerization degree of the polyvinyl alcohol is 1700; the alcoholysis degree is 99 percent;
(2) mixing 55 parts of polyoxytetramethylene glycol and 17 parts of hexamethylene diisocyanate at 75 ℃ for reaction for 4 hours, then adding 2 parts of trimethylolpropane at 85 ℃ for reaction for 6 hours, then adding 12 parts of hydroxypropyl methacrylate for heat preservation reaction for 1.5 hours, and adding 2 parts of triethylamine for neutralization after the reaction is finished to prepare a prepolymer;
(3) adding water into the prepolymer, stirring for 1.5h, and then adding 0.7 part of azobisisobutyronitrile and 7 parts of hydroxypropyl methacrylate to prepare a polyurethane acrylate emulsion with the solid content of 45 wt%;
(4) adding 12 wt% of oil film coated vermiculite into the polyurethane acrylate emulsion to prepare the intumescent flame retardant coating.
Example 2: a preparation method of an intumescent flame retardant coating comprises the following preparation steps:
(1) heating 30 parts of polyvinyl alcohol to 80 ℃, stirring and dissolving, then adding 2 parts of glycerol, 3 parts of linseed oil, 0.5 part of acetaldehyde and 0.5 part of tween 60, keeping the temperature and stirring for 0.5h, then cooling to 25 ℃, adding 10 parts of vermiculite, soaking for 2h, taking out and drying to obtain oil film coated vermiculite; wherein the polymerization degree of the polyvinyl alcohol is 1700; the alcoholysis degree is 98 percent;
(2) mixing 50 parts of polyoxytetramethylene glycol and 15 parts of hexamethylene diisocyanate at 65 ℃ for reaction for 6 hours, then adding 1.5 parts of trimethylolpropane at 80 ℃ for reaction for 7 hours, then adding 10 parts of hydroxypropyl methacrylate for heat preservation reaction for 1 hour, and adding 1 part of triethylamine for neutralization after the reaction is finished to prepare a prepolymer;
(3) adding water into the prepolymer, stirring for 1 hour, and then adding 0.5 part of azobisisobutyronitrile and 5 parts of hydroxypropyl methacrylate to prepare a polyurethane acrylate emulsion with the solid content of 40 wt%;
(4) and adding 10 wt% of oil film coated vermiculite into the polyurethane acrylate emulsion to prepare the intumescent flame retardant coating.
Example 3: a preparation method of an intumescent flame retardant coating comprises the following preparation steps:
(1) heating 50 parts of polyvinyl alcohol to 90 ℃, stirring and dissolving, then adding 5 parts of glycerol, 9 parts of linseed oil, 1 part of acetaldehyde and 1 part of tween 20, keeping the temperature and stirring for 1.5 hours, then cooling to 35 ℃, adding 15 parts of vermiculite, soaking for 2 hours, taking out and drying to obtain oil film coated vermiculite; wherein the polymerization degree of the polyvinyl alcohol is 1700; the alcoholysis degree is 99 percent;
(2) mixing 60 parts of polyoxytetramethylene glycol and 20 parts of hexamethylene diisocyanate at 85 ℃ for reaction for 2.5 hours, then adding 3 parts of trimethylolpropane at 90 ℃ for reaction for 4 hours, then adding 15 parts of hydroxypropyl methacrylate for heat preservation reaction for 2 hours, and adding 3 parts of triethylamine after the reaction is finished for neutralization to prepare a prepolymer;
(3) adding water into the prepolymer, stirring for 1.5h, and then adding 1 part of azobisisobutyronitrile and 8 parts of hydroxypropyl methacrylate to prepare a polyurethane acrylate emulsion with the solid content of 50 wt%;
(4) adding 15 wt% of oil film coated vermiculite into the polyurethane acrylate emulsion to prepare the intumescent flame retardant coating.
Example 4: the difference from example 1 is that the oil film coated vermiculite is modified by gel coating;
a preparation method of an intumescent flame retardant coating comprises the following preparation steps:
(1) heating 40 parts of polyvinyl alcohol to 85 ℃, stirring and dissolving, then adding 3 parts of glycerol, 6 parts of linseed oil, 0.8 part of acetaldehyde and 0.7 part of tween 80, keeping the temperature and stirring for 1 hour, then cooling to 30 ℃, adding 13 parts of vermiculite, soaking for 3 hours, taking out and drying to obtain oil film coated vermiculite; wherein the polymerization degree of the polyvinyl alcohol is 1700; the alcoholysis degree is 99 percent;
(2) mixing 55 parts of polyoxytetramethylene glycol and 17 parts of hexamethylene diisocyanate at 75 ℃ for reaction for 4 hours, then adding 2 parts of trimethylolpropane at 85 ℃ for reaction for 6 hours, then adding 12 parts of hydroxypropyl methacrylate for heat preservation reaction for 1.5 hours, and adding 2 parts of triethylamine for neutralization after the reaction is finished to prepare a prepolymer;
(3) adding water into the prepolymer, stirring for 1.5h, and then adding 0.7 part of azobisisobutyronitrile and 7 parts of hydroxypropyl methacrylate to prepare a polyurethane acrylate emulsion with the solid content of 45 wt%;
(4) adding 12 wt% of oil film coated vermiculite into the polyurethane acrylate emulsion to prepare the intumescent flame retardant coating;
the oil film coated vermiculite is modified by gel coating, and comprises the following steps:
a: putting hydroxymethyl cellulose into water to prepare a hydroxymethyl cellulose aqueous solution with the concentration of 3%;
b: placing oil film coated vermiculite in a hydroxymethyl cellulose aqueous solution, uniformly stirring to obtain a mixed solution, and then dropping the mixed solution into methanol to prepare wet gel, wherein the mass ratio of the oil film coated vermiculite to the hydroxymethyl cellulose is 1: 1.7;
c: and (3) carrying out solvent replacement, freeze drying and grinding on the wet gel to prepare the oil film coated vermiculite cellulose gel.
Example 5: the difference from example 1 is that the oil film coated vermiculite is modified by gel coating;
a preparation method of an intumescent flame retardant coating comprises the following preparation steps:
(1) heating 40 parts of polyvinyl alcohol to 85 ℃, stirring and dissolving, then adding 3 parts of glycerol, 6 parts of linseed oil, 0.8 part of acetaldehyde and 0.7 part of tween 80, keeping the temperature and stirring for 1 hour, then cooling to 30 ℃, adding 13 parts of vermiculite, soaking for 3 hours, taking out and drying to obtain oil film coated vermiculite; wherein the polymerization degree of the polyvinyl alcohol is 1700; the alcoholysis degree is 99 percent;
(2) mixing 55 parts of polyoxytetramethylene glycol and 17 parts of hexamethylene diisocyanate at 75 ℃ for reaction for 4 hours, then adding 2 parts of trimethylolpropane at 85 ℃ for reaction for 6 hours, then adding 12 parts of hydroxypropyl methacrylate for heat preservation reaction for 1.5 hours, and adding 2 parts of triethylamine for neutralization after the reaction is finished to prepare a prepolymer;
(3) adding water into the prepolymer, stirring for 1.5h, and then adding 0.7 part of azobisisobutyronitrile and 7 parts of hydroxypropyl methacrylate to prepare a polyurethane acrylate emulsion with the solid content of 45 wt%;
(4) adding 12 wt% of oil film coated vermiculite into the polyurethane acrylate emulsion to prepare the intumescent flame retardant coating;
the oil film coated vermiculite is modified by gel coating, and comprises the following steps:
a: putting hydroxymethyl cellulose into water to prepare a 2% hydroxymethyl cellulose aqueous solution;
b: placing oil film coated vermiculite in a hydroxymethyl cellulose aqueous solution, uniformly stirring to obtain a mixed solution, and then dropping the mixed solution into methanol to prepare wet gel, wherein the mass ratio of the oil film coated vermiculite to the hydroxymethyl cellulose is 1: 1.5;
c: and (3) carrying out solvent replacement, freeze drying and grinding on the wet gel to prepare the oil film coated vermiculite cellulose gel.
Example 6: the difference from example 1 is that the oil film coated vermiculite is modified by gel coating;
a preparation method of an intumescent flame retardant coating comprises the following preparation steps:
(1) heating 40 parts of polyvinyl alcohol to 85 ℃, stirring and dissolving, then adding 3 parts of glycerol, 6 parts of linseed oil, 0.8 part of acetaldehyde and 0.7 part of tween 80, keeping the temperature and stirring for 1 hour, then cooling to 30 ℃, adding 13 parts of vermiculite, soaking for 3 hours, taking out and drying to obtain oil film coated vermiculite; wherein the polymerization degree of the polyvinyl alcohol is 1700; the alcoholysis degree is 99 percent;
(2) mixing 55 parts of polyoxytetramethylene glycol and 17 parts of hexamethylene diisocyanate at 75 ℃ for reaction for 4 hours, then adding 2 parts of trimethylolpropane at 85 ℃ for reaction for 6 hours, then adding 12 parts of hydroxypropyl methacrylate for heat preservation reaction for 1.5 hours, and adding 2 parts of triethylamine for neutralization after the reaction is finished to prepare a prepolymer;
(3) adding water into the prepolymer, stirring for 1.5h, and then adding 0.7 part of azobisisobutyronitrile and 7 parts of hydroxypropyl methacrylate to prepare a polyurethane acrylate emulsion with the solid content of 45 wt%;
(4) adding 12 wt% of oil film coated vermiculite into the polyurethane acrylate emulsion to prepare the intumescent flame retardant coating;
the oil film coated vermiculite is modified by gel coating, and comprises the following steps:
a: putting hydroxymethyl cellulose into water to prepare a 4% hydroxymethyl cellulose aqueous solution;
b: placing oil film coated vermiculite in a hydroxymethyl cellulose aqueous solution, uniformly stirring to obtain a mixed solution, and then dropping the mixed solution into methanol to prepare wet gel, wherein the mass ratio of the oil film coated vermiculite to the hydroxymethyl cellulose is 1: 2;
c: and (3) carrying out solvent replacement, freeze drying and grinding on the wet gel to prepare the oil film coated vermiculite cellulose gel.
Example 7: the difference from the example 4 is that the oil film coated vermiculite cellulose gel is modified by expansion:
putting hexamethylene diisocyanate into toluene, and dropwise adding monolauryl phosphate at 70 ℃ under the protection of nitrogen for reacting for 6 hours to prepare an intermediate product reaction liquid; placing the oil film coated vermiculite cellulose gel into an intermediate product reaction solution, continuously reacting for 6h at 70 ℃ under the protection of nitrogen, washing, and then carrying out vacuum freeze drying to prepare the expansion modified oil film coated vermiculite cellulose gel; wherein the molar ratio of the hexamethylene diisocyanate to the monolauryl phosphate is 3:1, and the mass ratio of the oil film coated vermiculite cellulose gel to the hexamethylene diisocyanate is 1: 1.2.
Example 8: the difference from the example 4 is that the oil film coated vermiculite cellulose gel is modified by expansion:
putting hexamethylene diisocyanate into toluene, and dropwise adding monolauryl phosphate to react for 7 hours at 65 ℃ under the protection of nitrogen to prepare an intermediate product reaction liquid; placing the oil film coated vermiculite cellulose gel into an intermediate product reaction solution, continuously reacting for 7h at 65 ℃ under the protection of nitrogen, washing, and then carrying out vacuum freeze drying to prepare the expansion modified oil film coated vermiculite cellulose gel; wherein the molar ratio of the hexamethylene diisocyanate to the monolauryl phosphate is 2:1, and the mass ratio of the oil film coated vermiculite cellulose gel to the hexamethylene diisocyanate is 1:1.
Example 9: the difference from the example 4 is that the oil film coated vermiculite cellulose gel is modified by expansion:
putting hexamethylene diisocyanate into toluene, and dropwise adding monolauryl phosphate to react for 4 hours at 75 ℃ under the protection of nitrogen to prepare an intermediate product reaction liquid; placing the oil film coated vermiculite cellulose gel into an intermediate product reaction solution, continuously reacting for 4 hours at 75 ℃ under the protection of nitrogen, washing, and then carrying out vacuum freeze drying to prepare the expansion modified oil film coated vermiculite cellulose gel; wherein the molar ratio of the hexamethylene diisocyanate to the monolauryl phosphate is 5:1, and the mass ratio of the oil film coated vermiculite cellulose gel to the hexamethylene diisocyanate is 1: 1.3.
Comparative example 1: the difference from example 1 is that no vermiculite was added to the coating.
A preparation method of a polyurethane acrylate emulsion comprises the following preparation steps:
(1) mixing 55 parts of polyoxytetramethylene glycol and 17 parts of hexamethylene diisocyanate at 75 ℃ for reaction for 4 hours, then adding 2 parts of trimethylolpropane at 85 ℃ for reaction for 6 hours, then adding 12 parts of hydroxypropyl methacrylate for heat preservation reaction for 1.5 hours, and adding 2 parts of triethylamine for neutralization after the reaction is finished to prepare a prepolymer;
(2) adding water into the prepolymer, stirring for 1.5h, and then adding 0.7 part of azobisisobutyronitrile and 7 parts of hydroxypropyl methacrylate to prepare the polyurethane acrylate emulsion with the solid content of 45 wt%.
Comparative example 2: the difference from the example 1 is that the vermiculite added in the coating is not coated by an oil film
A preparation method of an intumescent flame retardant coating comprises the following preparation steps:
(1) mixing 55 parts of polyoxytetramethylene glycol and 17 parts of hexamethylene diisocyanate at 75 ℃ for reaction for 4 hours, then adding 2 parts of trimethylolpropane at 85 ℃ for reaction for 6 hours, then adding 12 parts of hydroxypropyl methacrylate for heat preservation reaction for 1.5 hours, and adding 2 parts of triethylamine for neutralization after the reaction is finished to prepare a prepolymer;
(2) adding water into the prepolymer, stirring for 1.5h, and then adding 0.7 part of azobisisobutyronitrile and 7 parts of hydroxypropyl methacrylate to prepare a polyurethane acrylate emulsion with the solid content of 45 wt%;
(3) 12 wt% of vermiculite is added into the polyurethane acrylate emulsion to prepare the intumescent flame retardant coating.
Comparative example 3: the difference from the embodiment 7 is that when the oil film coated vermiculite cellulose gel is subjected to expansion modification, the molar weight of the hexamethylene diisocyanate is less than that of the monolauryl phosphate
The oil film coated vermiculite cellulose gel expansion modification steps are as follows: putting hexamethylene diisocyanate into toluene, and dropwise adding monolauryl phosphate at 70 ℃ under the protection of nitrogen for reacting for 6 hours to prepare an intermediate product reaction liquid; placing the oil film coated vermiculite cellulose gel into an intermediate product reaction solution, continuously reacting for 6h at 70 ℃ under the protection of nitrogen, washing, and then carrying out vacuum freeze drying to prepare the expansion modified oil film coated vermiculite cellulose gel; wherein the molar ratio of the hexamethylene diisocyanate to the monolauryl phosphate is 2:3, and the mass ratio of the oil film coated vermiculite cellulose gel to the hexamethylene diisocyanate is 1: 1.2.
The coatings prepared in the above examples and comparative examples were formed into coatings (3mm) and tested for properties, the results of which are shown in the following table.
Note: the fire performance test is in accordance with GB 51249-2017.
As can be seen from the above table, compared with the urethane acrylate coating prepared without adding vermiculite in the comparative example 1, the flame retardant coatings prepared in the examples 1-3 have higher hardness, more improved oxygen index, large expansion thickness after fire, and long fire resistance limit time; the coating prepared in the comparative example 2 has reduced expansion thickness and fire-resistant limit time because the added vermiculite is not coated with an oil film; in the coating prepared in the embodiment 4, oil film coated vermiculite is modified by gel coating, so that the uniformity of an expansion layer is improved, and the fireproof performance is improved; the oil film-coated vermiculite cellulose gel in the coating prepared in the embodiment 7 is subjected to expansion modification, so that the expansion thickness is increased, and the fireproof performance is improved; in contrast, in comparative example 3, when the oil film-coated vermiculite cellulose gel is subjected to expansion modification, the molar weight of hexamethylene diisocyanate is less than that of monolauryl phosphate, so that effective modification cannot be performed, and the fire resistance is not obviously improved compared with that of example 7.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The preparation method of the intumescent flame retardant coating is characterized by comprising the following preparation steps:
(1) heating 30-50 parts of polyvinyl alcohol to 80-90 ℃, stirring for dissolving, then adding 2-5 parts of glycerol, 3-9 parts of linseed oil, 0.5-1 part of acetaldehyde and 0.5-1 part of emulsifier, keeping the temperature, stirring for 0.5-1.5h, then cooling to 25-35 ℃, adding 10-15 parts of vermiculite, soaking for 2-4h, taking out and drying to obtain oil film coated vermiculite;
(2) mixing 50-60 parts of polyoxytetramethylene glycol and 15-20 parts of hexamethylene diisocyanate at 65-85 ℃ for reaction for 2.5-6h, then adding 1.5-3 parts of trimethylolpropane at 80-90 ℃ for reaction for 4-7h, then adding 10-15 parts of hydroxypropyl methacrylate for heat preservation reaction for 1-2h, and adding 1-3 parts of triethylamine for neutralization after the reaction is finished to prepare a prepolymer;
(3) adding water into the prepolymer, stirring for 1-1.5h, and then adding 0.5-1 part of azodiisobutyronitrile and 5-8 parts of hydroxypropyl methacrylate to prepare a polyurethane acrylate emulsion;
(4) and adding an oil film to coat vermiculite into the polyurethane acrylate emulsion to prepare the intumescent flame retardant coating.
2. A process for the preparation of an intumescent, flame retardant coating according to claim 1, characterized in that in step (1) the degree of polymerization of said polyvinyl alcohol is 1700; the alcoholysis degree is 98-99%.
3. The process of claim 1, wherein the emulsifier in step (1) comprises one or more of tween 20, tween 60 or tween 80.
4. The process according to claim 1, wherein the polyurethane acrylate emulsion in step (3) has a solids content of 40-50 wt%.
5. The process according to claim 1, wherein 10-15 wt% oil film coated vermiculite is added in step (4).
6. A method of preparing an intumescent fire retardant coating according to claims 1-5, wherein the oil film coated vermiculite is modified by gel coating, comprising the steps of:
a: putting hydroxymethyl cellulose into water to prepare a 2-4% hydroxymethyl cellulose aqueous solution;
b: putting the oil film coated vermiculite into a hydroxymethyl cellulose aqueous solution, uniformly stirring to obtain a mixed solution, and then dripping the mixed solution into a coagulating bath to prepare wet gel;
c: and (3) carrying out solvent replacement, freeze drying and grinding on the wet gel to prepare the oil film coated vermiculite cellulose gel.
7. The preparation method of the intumescent flame retardant coating of claim 6, characterized in that the mass ratio of the oil film coated vermiculite to the hydroxymethyl cellulose is 1: 1.5-2.
8. The process for preparing an intumescent flame retardant coating according to claim 6, characterized in that said oil film coated vermiculite cellulose gel is modified by expansion: putting hexamethylene diisocyanate into toluene, and dropwise adding monolauryl phosphate to react for 4-7h at 65-75 ℃ under the protection of nitrogen to prepare an intermediate product reaction solution; and (3) placing the oil film coated vermiculite cellulose gel into an intermediate product reaction solution, continuously reacting for 4-7h at 65-75 ℃ under the protection of nitrogen, washing, and then carrying out vacuum freeze drying to prepare the expansion modified oil film coated vermiculite cellulose gel.
9. The process according to claim 8, wherein the molar ratio of hexamethylene diisocyanate to monolauryl phosphate is 2-5: 1.
10. The process according to claim 8, wherein the mass ratio of oil film-coated vermiculite cellulose gel to hexamethylene diisocyanate is 1: 1-1.3.
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