CN108610755B - Water-based phase-change heat-absorbing expansion type tunnel flame-retardant fireproof coating and preparation method thereof - Google Patents
Water-based phase-change heat-absorbing expansion type tunnel flame-retardant fireproof coating and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a water-based phase-change heat-absorption intumescent flame-retardant fireproof coating for a tunnel, which comprises the following raw materials: the preparation method comprises the following steps of loading mannitol-galactose on expanded perlite, loading melamine-phosphoric acid modified lignin, loading chlorinated paraffin on expanded graphite, gelatinized starch, light-burned magnesium oxide, magnesium chloride, polyoxyethylene ether oleate dustproof agent, organic silicon defoaming agent, hydroxyl silicone oil, amino silicone oil, waterborne polyurethane, nano tin dioxide, titanium dioxide, filler, aluminum silicate and polyether modified polydimethylsiloxane leveling agent. This fire-retardant fireproof coating absorbs latent heat at the conflagration initial stage and resists the temperature rise, forms the isolated heat of expanded foam charcoal layer under the high temperature effect, prevents the temperature rise of tunnel concrete structure, avoids the intensity decline of tunnel concrete structure, and the coating is thin, construction speed is fast, the maintenance cycle is short, the water proofness is good, be applicable to the dark humid environment in tunnel.
Description
Technical Field
The invention belongs to the field of functional coating manufacturing, and particularly relates to a water-based phase-change heat-absorption intumescent flame-retardant fireproof coating for a tunnel and a preparation method thereof.
Background
In the tunnel after the second Guangdong high-speed rock in 3/1/2014, two articulated trains for transporting methanol collide with each other, the methanol in the front train leaks, fires and burns, and other two dangerous chemical transport vehicles, 31 coal transport vehicles and other vehicles which are detained in the tunnel are ignited and detonated, so that 40 people die, 12 people are injured, 42 vehicles are burnt, and the direct economic loss is 8197 ten thousand yuan.
Once a fire disaster occurs in the tunnel, the fire disaster not only can cause casualties and vehicle loss of people, but also can cause damage to important infrastructure of the tunnel which is related to local economic life-lines, and the serious possibility can cause the damage of the structure in the tunnel and the incapability of repairing the tunnel, thereby causing huge social influence and economic loss. For tunnel fire prevention, on one hand, prevention needs to be enhanced in operation, and on the other hand, disaster resistance needs to be improved in design and construction.
The research of American national standards and test Association shows that when the fire temperature of a tunnel rises to 600 ℃, the strength loss of concrete reaches more than 50%, the yield stress of steel is reduced to below 1/3 of the yield stress at normal temperature, the fire duration in the tunnel exceeds 90min, the temperature reaches more than 1000 ℃, the tunnel masonry is difficult to bear the high temperature, and the serious part of the tunnel masonry can be collapsed or burst; in addition, the tunnel environment is relatively closed, the people flow density is high, once a fire disaster happens, evacuation and rescue are quite difficult, and serious casualties and property loss are easily caused. Therefore, it is very important to perform fire protection treatment on the tunnel. In various industrial accidents, the fire accidents of the road and subway train tunnels are the most difficult to rescue, the driving interruption time is the longest, and the economic loss is the greatest.
Therefore, the fireproof coating is adopted to protect the tunnel, has important effects of delaying the propagation speed of fire and preventing the tunnel from collapsing, wins precious time for the safe evacuation of people and the rescue of the fire, and is an effective means for maintaining the fire prevention safety of the tunnel. The tunnel fireproof coating is coated on the side wall and the vault of the tunnel, plays a role in protecting the side wall and the vault of the tunnel from heat insulation and fire prevention, and avoids strength reduction, burst and lining reinforcing steel bar damage of the reinforced concrete structure in the tunnel in case of fire.
The Chinese invention patent 201010200026.2 discloses a tunnel fire-retardant coating and its preparation and construction process, which is composed of 582 resin, portland cement, sepiolite, ammonium dichromate, light calcium carbonate, aluminum silicate, fly ash hollow floating bead, wollastonite powder, pottery clay, cellulose ether, concrete expanding agent, tin oxide and polypropylene fiber; the fireproof coating is put into a V-shaped forced mixer according to the component proportion, and is stirred for 10-15 minutes to prepare a powdery mixture; stirring water and the fireproof coating powder into thick paste according to the weight ratio of 0.8-0.85; spraying is carried out from the waist part to the top part of the tunnel from bottom to top by a sprayer to reach a preset thickness.
The invention of Chinese patent 200310115526.6 discloses a tunnel fire-proof paint and its manufacturing process, which adopts high molecular polymer adhesive modified silicate, phosphate inorganic adhesive, combines the advantages of organic high molecular and inorganic materials, the interaction of two active components, and the cooperation with high temperature resistant aluminum silicate fiber to strengthen, improves the bonding performance of the fire-proof coating and the inner wall of the tunnel reinforced concrete, improves the tensile strength and bending strength of the fire-proof coating, and prevents the problems of volume shrinkage, cracking and the like in the curing process of the tunnel fire-proof paint; meanwhile, the polymer emulsion has the functions of reducing water, preventing water and the like, and further a fireproof coating with excellent performance is obtained. The components and the proportion are as follows; 37.7-43.3 parts of silicate and phosphate binder, 5-10 parts of polymer emulsion, 18.7-34.9 parts of aggregate, 3.7-6.2 parts of reinforcing fiber and 34.7-50 parts of flame retardant.
The Chinese invention patent 200610021101.2 discloses an expandable graphite-rubber powder system thin-layer tunnel fireproof coating, which adopts re-dispersible latex powder as an adhesive to improve the bonding strength of a coating, and adopts expandable graphite as a flame-retardant heat-insulating material to realize higher fire-resistant limit of the thin coating. The composition and the proportion are as follows: 40-50 parts of redispersible latex powder, 30-50 parts of expandable graphite, 5 parts of aluminum hydroxide, 10-15 parts of magnesium hydroxide and 5-10 parts of waterproof powder.
Chinese invention patent 201310603177.6 discloses an intumescent tunnel fire retardant coating, which comprises the following main raw materials: 86-90 parts of refractory cement, 36-48 parts of AEC expanded cement, 26-38 parts of polyvinyl acetate emulsion, 20-30 parts of urea-formaldehyde resin, 6-8 parts of aluminum hydroxide, 10-16 parts of sepiolite, 6-8 parts of perlite, 10-14 parts of fly ash, 10-14 parts of polypropylene short fiber, 10-15 parts of carboxymethyl cellulose, 5-9 parts of fatty alcohol-polyoxyethylene ether, 6-8 parts of fly ash glass beads, 10-16 parts of kaolin and 5-7 parts of ammonium polyphosphate.
The tunnel fireproof paint is widely applied in China, and is mainly a thick inorganic material at present, cement is generally used as a cementing material, and light aggregates such as expanded perlite and expanded vermiculite are used as heat-insulating materials to form a thicker non-combustible heat-insulating layer with low heat conductivity coefficient, so that the aim of protecting the tunnel from fire is fulfilled. However, in application, due to the large construction thickness and poor adhesion of the material, the fireproof layer of the tunnel is cracked and broken, so that potential safety hazards are brought to driving; secondly, the flatness of the material is poor, which affects the beauty of the tunnel.
Therefore, the research of the special thin phase-change heat-absorption expansion fireproof coating for the tunnel, which has the advantages of thin coating, high construction speed, short maintenance period and good water resistance and is suitable for the dark and humid environment of the tunnel, can certainly generate great economic and social benefits.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects and defects in the background technology and provides a thin phase change heat absorption expansion type flame retardant fireproof coating special for a tunnel, which is used for inhibiting flame through medium-low temperature phase change heat absorption and protecting an internal reinforced concrete structure through high-temperature expansion carbon layer heat insulation, and a preparation method thereof.
Compared with the non-intumescent tunnel flame-retardant fireproof coating, the intumescent fireproof coating has the advantages of small using amount, thin coating, good fire resistance, high bonding strength, short maintenance period, high construction efficiency and the like, and is widely applied to the hydrocarbon fire resistance of tunnels.
The intumescent flame retardant has three basic elements of an acid source, a carbon source and an air source. An acid source at a temperature in the range of 150 ℃ to produce an acid capable of esterifying the polyol and which can act as a dehydrating agent; at a slightly higher temperature, acid and a carbon source are subjected to esterification reaction, and amino in the system is used as a catalyst of the esterification reaction to accelerate the reaction; the resin system is melted before and during the esterification reaction, the resin system in a molten state is expanded and foamed by the incombustible gas generated in the reaction process, and meanwhile, the polyhydric alcohol and the ester are dehydrated and carbonized to form inorganic matters and carbon residues, so that the system is further foamed; when the reaction is nearly completed, the system is gelled and solidified, and finally a porous foam carbon layer is formed. The foam carbon layer formed by the synergistic action of the intumescent flame retardant and the resin under the fire condition has the effects of heat insulation, oxygen isolation, smoke suppression, drip prevention and the like, and is a green high-efficiency flame-retardant technical method with low smoke, low toxicity and no corrosive gas.
Phase change materials have the ability to change their physical state over a range of temperatures. Taking solid-liquid phase change as an example, when the material is heated to a melting temperature, the material generates phase change from a solid state to a liquid state, and in the melting process, the phase change material absorbs and stores a large amount of latent heat; when the phase change material is cooled, the stored heat is dissipated to the environment within a certain temperature range, and reverse phase change from liquid to solid is carried out. In both phase change processes, the stored or released energy is called latent heat of phase change. When the physical state changes, the temperature of the material is almost kept unchanged before the phase change is completed, a wide temperature platform is formed, and although the temperature is unchanged, the latent heat absorbed or released is quite large.
In order to solve the technical problems, the technical scheme provided by the invention is to provide a water-based phase-change heat-absorption expansion type tunnel flame-retardant fireproof coating, which comprises the following raw materials in parts by mass: 20-30 parts of expanded perlite loaded mannitol-galactose, 5-15 parts of melamine-phosphoric acid modified lignin, 5-15 parts of expanded graphite loaded chlorinated paraffin, 35-55 parts of gelatinized starch, 5-15 parts of light-burned magnesium oxide, 3-8 parts of magnesium chloride, 2-4 parts of polyoxyethylene ether oleate dustproof agent, 0.1-1.0 part of organic silicon defoamer, 0.5-2.0 parts of hydroxyl silicone oil, 0.1-1.0 part of amino silicone oil, 5-15 parts of waterborne polyurethane, 5-25 parts of nano tin dioxide, 5-10 parts of titanium dioxide, 20-40 parts of filler, 5-10 parts of aluminum silicate and 0.10-0.15 part of polyether modified polydimethylsiloxane leveling agent;
the expanded perlite loaded mannitol-galactose is obtained by reacting expanded perlite, mannitol, galactose and hydroxyl silicone oil, the melamine-phosphoric acid modified lignin is obtained by reacting melamine, a sodium hydroxide solution, formaldehyde, lignin, a phosphoric acid solution, urea and hydrogen peroxide, the expanded graphite loaded chlorinated paraffin is obtained by reacting expanded graphite, chlorinated paraffin 42 and the hydroxyl silicone oil, and the gelatinized starch is obtained by reacting starch, water and liquefied α -amylase.
The above tunnel fire-retardant fireproof coating is preferably prepared from the following components, by mass, 10-20 parts of expanded perlite, 30-40 parts of mannitol, 10-20 parts of galactose and 0.1-1.0 parts of hydroxyl silicone oil; according to the invention, the phase-change heat absorption system is formed by loading mannitol-galactose on the expanded perlite, mannitol melts and absorbs heat at 167 ℃, phase-change heat reaches 326.8J/g, galactose melting point is 188 ℃, and melting heat is 351.8J/g, so that the phase-change heat absorption is huge, and the cooling and fireproof effects are obvious, therefore, the temperature rise of the coating and the internal concrete structure thereof can be effectively prevented under the fire condition, the burning chance of the coating is inhibited and reduced, and the fire is avoided.
The mass ratio of the melamine to the sodium hydroxide solution to the formaldehyde to the lignin to the phosphoric acid solution to the urea to the hydrogen peroxide is (10-15): (1.5-2.5): 6-10): 40-60): 10-12): 0.5-15): 1-5, the concentration of the sodium hydroxide solution is 0.1-1.0mol/L, the mass concentration of the formaldehyde is 37%, the mass concentration of the phosphoric acid solution is 50-85%, and the mass concentration of the hydrogen peroxide is 3%; according to the invention, the melamine-phosphoric acid modified lignin is used for forming an expansion flame-retardant system, and the expansion flame-retardant system is carbonized and expanded at about 250 ℃ to form an expansion foam carbon layer, so that heat transfer can be effectively isolated; meanwhile, oxygen can be isolated, the release of combustible gas is blocked, the development of small fire is inhibited to form big fire, and the fire occurrence chance and the fire loss are effectively reduced.
The mass ratio of the expanded graphite to the chlorinated paraffin 42 to the hydroxyl silicone oil is (10-20) to (80-90) to (0.1-1.0);
the mass ratio of the starch to the water to the liquefied α -amylase is (10-15) to 20:0.006, and the adhesive takes the gelatinized starch, the waterborne polyurethane and the magnesium oxychloride hydrogel as the bonding components of the tunnel flame-retardant fireproof coating, and has high bonding strength, water resistance, moisture resistance, heat insulation and sound insulation through hybrid crosslinking of inorganic and organic components.
Preferably, the filler comprises, by mass, 5-10 parts of sepiolite, 5-10 parts of glass hollow floating beads, 5-10 parts of kaolin and 5-10 parts of slag wool. The invention selects expandable graphite, perlite, sepiolite, slag wool and hollow glass floating beads as fillers, which are subjected to expansion reaction during high-temperature firing to absorb expansion phase change heat, and the expansion of the fillers leads to thickening of a foam carbon layer and enhancement of heat insulation, so that the thickness of the coating can be greatly reduced under the same fire-resistant requirement.
The tunnel flame-retardant fireproof coating integrates the technologies of 'phase change heat absorption flame suppression', 'expanded carbon layer heat insulation protection' and the like, can realize high-efficiency flame retardance and fire prevention, namely latent heat is absorbed by phase change energy storage materials such as mannitol, galactose and the like at the initial stage of fire to resist temperature rise, the heat is isolated by an expanded foam carbon layer formed by a melamine-phosphoric acid modified lignin and starch flame-retardant system under the action of high temperature, heat transmission is isolated by the aid of expandable graphite, expanded perlite, sepiolite, slag wool and glass hollow floating beads, temperature rise of a tunnel concrete structure is prevented, strength reduction of the tunnel concrete structure is avoided, the expansion multiplying power of the prepared tunnel flame-retardant fireproof coating is more than 15 times, the fire-resistant limit time of a 5.0mm coating is more than 150min, and the coating is thin, high in construction speed, short in maintenance period, good in water resistance, The tunnel is suitable for the dark and humid environment of the tunnel.
Based on a general technical concept, the invention also correspondingly provides a preparation method of the water-based phase-change heat-absorption intumescent flame-retardant fireproof coating for the tunnel, which comprises the following steps:
(1) heating the expanded perlite, vacuumizing, adding mannitol and galactose which are melted under the protection of nitrogen, preserving heat under the protection of nitrogen for reaction, cooling the obtained product to room temperature, adding hydroxyl silicone oil, and grinding to obtain expanded perlite loaded mannitol-galactose;
(2) mixing and stirring melamine and a sodium hydroxide solution uniformly, adding formaldehyde while stirring, and heating to perform a first reflux reaction to obtain a melamine formaldehyde prepolymer; adding a phosphoric acid solution, urea and hydrogen peroxide into lignin while stirring, stirring to perform a phosphorylation reaction, adding the melamine formaldehyde prepolymer while stirring after the reaction is completed, and continuously stirring and heating to perform a second reflux reaction to obtain melamine-phosphoric acid modified lignin;
(3) heating the expanded graphite, vacuumizing, adding chlorinated paraffin 42, keeping the temperature at normal pressure for reaction, cooling the product to room temperature after the reaction is finished, adding hydroxyl silicone oil, and grinding to obtain expanded graphite loaded chlorinated paraffin;
(4) adding starch into water, stirring to obtain starch slurry, adjusting pH to weak acidity, adding CaCl
2Stirring and heating the solution, adding the liquefied α -amylase after the starch slurry is completely pasty, continuously stirring to liquefy the starch, and keeping the temperature to react to obtain gelatinized starch;
(5) mixing the expanded perlite loaded with mannitol-galactose obtained in the step (1), the melamine-phosphoric acid modified lignin obtained in the step (2), the expanded graphite loaded with chlorinated paraffin obtained in the step (3), the gelatinized starch obtained in the step (4), light-burned magnesium oxide, magnesium chloride, polyoxyethylene ether oleate dustproof agent, organic silicon defoamer, hydroxyl silicone oil and amino silicone oil, performing first shearing and stirring, adding waterborne polyurethane, nano tin dioxide, titanium dioxide, sepiolite, glass hollow floating beads, kaolin, slag wool, aluminum silicate and modified polydimethylsiloxane leveling agent, continuing to perform second shearing and stirring, and sieving with a 200-mesh sieve to obtain the waterborne phase-change heat absorption expanded tunnel flame-retardant fireproof coating.
Preferably, in the step (1), the heating temperature of the expanded perlite is 70-90 ℃, the vacuumizing is carried out to 20-50kPa, the vacuumizing time is 10-30min, the pressure of nitrogen is 2atm, the heat preservation temperature is 70-90 ℃, the heat preservation time is 40-80min, and the grinding time is 1.0-3.0 h.
Preferably, in the step (2), the heating temperature of the first reflux reaction is 40-60 ℃, and the reaction time is 110-130 min; the temperature of the phosphorylation reaction is 70-90 ℃, and the reaction time is 1-5 h; the temperature of the second reflux reaction is 70-90 ℃, and the reaction time is 80-100 min.
Preferably, in the step (3), the heating temperature of the expanded graphite is 70-90 ℃, the vacuumizing is carried out to 20-50kPa, the vacuumizing time is 10-30min, the temperature of the normal pressure heat preservation is 70-90 ℃, the reaction time is 40-80min, and the grinding time is 1.0-3.0 h.
Preferably, in the step (4), Na with the mass concentration of 5% is adopted
2CO
3Adjusting pH to 6.2-6.3 with CaCl
2The mass concentration of the solution is 5 percent, the stirring and heating temperature is 90-95 ℃, the heat preservation temperature is 70-80 ℃, and the reaction time is 0.5-2 h.
Preferably, in the step (5), the fineness of the titanium dioxide is 400 meshes, the fineness of the sepiolite, the glass hollow floating beads, the kaolin and the slag wool are all 200 meshes, and the fineness of the aluminum silicate is 2000 meshes.
Preferably, in the step (5), the rotation speed of the first shearing and the second shearing are both 500-.
Compared with the prior art, the invention has the beneficial effects that:
1. the tunnel flame-retardant fireproof coating integrates the technologies of 'phase change heat absorption flame suppression', 'expanded carbon layer heat insulation protection' and the like, can realize high-efficiency flame retardance and fire prevention, namely latent heat is absorbed by phase change energy storage materials such as mannitol, galactose and the like at the initial stage of fire to resist temperature rise, the heat is isolated by an expanded foam carbon layer formed by a melamine-phosphoric acid modified lignin and starch flame-retardant system under the action of high temperature, heat transmission is isolated by the aid of expandable graphite, expanded perlite, sepiolite, slag wool and glass hollow floating beads, temperature rise of a tunnel concrete structure is prevented, strength reduction of the tunnel concrete structure is avoided, the expansion multiplying power of the prepared tunnel flame-retardant fireproof coating is more than 15 times, the fire-resistant limit time of a 5.0mm coating is more than 150min, and the coating is thin, high in construction speed, short in maintenance period, good in water resistance, The tunnel is suitable for the dark and humid environment of the tunnel.
2. According to the invention, the phase-change heat absorption system is formed by loading mannitol-galactose on the expanded perlite, mannitol melts and absorbs heat at 167 ℃, phase-change heat reaches 326.8J/g, galactose melting point is 188 ℃, and melting heat is 351.8J/g, so that the phase-change heat absorption is huge, and the cooling and fireproof effects are obvious, therefore, the temperature rise of the coating and the internal concrete structure thereof can be effectively prevented under the fire condition, the burning chance of the coating is inhibited and reduced, and the fire is avoided.
3. According to the invention, an expansion flame-retardant system is formed by utilizing melamine-phosphoric acid modified lignin, and the expansion flame-retardant system is carbonized and expanded at about 250 ℃ to form an expansion foam carbon layer, so that heat transfer can be effectively isolated by cooperating with chlorinated paraffin and aluminum silicate; meanwhile, oxygen can be isolated, the release of combustible gas is blocked, the development of small fire is inhibited to form big fire, and the fire occurrence chance and the fire loss are effectively reduced.
4. The invention takes the gelatinized starch, the waterborne polyurethane and the magnesium oxychloride hydrogel as the bonding components of the tunnel flame-retardant fireproof coating, and has high bonding strength, water resistance, moisture resistance, heat insulation and sound insulation through hybrid crosslinking of inorganic-organic components.
5. The invention uses the nano tin dioxide as the smoke inhibitor, and has the functions of converting and inhibiting smoke and reducing smoke toxicity under the fire condition in cooperation with the titanium dioxide, the expanded graphite, the slag wool and the sepiolite; the nano tin dioxide also has small-size effect, quantum size effect, surface effect and macroscopic quantum tunneling effect, and has good permeability to visible light; meanwhile, the titanium dioxide and the nano tin dioxide have the effects of mildew prevention, sterilization and self cleaning, and can effectively resist the invasion of mildew.
6. The invention selects expandable graphite, perlite, sepiolite, slag wool, kaolin and glass hollow floating beads as the fillers, the fillers are subjected to expansion reaction when being burnt at high temperature to absorb expansion phase change heat, and the expansion of the fillers causes the thickening of a foam carbon layer and the enhancement of heat insulation, so that the thickness of the coating can be greatly reduced under the condition of the same fire resistance requirement.
Detailed Description
In order to facilitate an understanding of the present invention, the present invention will be described more fully and in detail with reference to the preferred embodiments, but the scope of the present invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
the invention relates to a water-based phase-change heat-absorption intumescent flame-retardant fireproof coating for a tunnel, which comprises the following steps:
(1) heating 8.0kg of expanded perlite in a reactor to 80 ℃, simultaneously vacuumizing to 40kPa, preserving heat and vacuumizing for 20min, then adding 20kg of mannitol and 10kg of galactose which are molten under the protection of nitrogen, preserving heat and reacting at 80 ℃ for 60min under the protection of 2atm nitrogen, cooling the product to room temperature, adding 200g of hydroxyl silicone oil, and grinding in a planetary ball mill for 2.0h to obtain expanded perlite loaded with mannitol-galactose;
(2) adding 12kg of melamine and 2.0L of 0.5mol/L NaOH solution into a reaction kettle, uniformly stirring, slowly adding 8.0L of 37% formaldehyde while stirring, heating to 50 ℃, and carrying out a first stirring reflux reaction for 120min to obtain a melamine-formaldehyde prepolymer; 40kg of lignin was added to a reaction kettle, and 11kg of 85% H was added with stirring
3PO
4Stirring the solution, 10kg of urea and 2.0L of 3% hydrogen peroxide at 80 ℃ to perform dry type phosphorylation reaction for 3.5 hours; adding the melamine formaldehyde prepolymer under stirring, continuously stirring and heating to 80 ℃ to carry out secondary reflux reaction for 90min to obtain melamine-phosphoric acid modified lignin;
(3) heating 8.0kg of expanded graphite in a reactor to 80 ℃, simultaneously vacuumizing to 40kPa, preserving heat and vacuumizing for 20min, then adding 40kg of chlorinated paraffin cp42, preserving heat at normal pressure and 80 ℃, reacting for 60min, cooling a product to room temperature, adding 200g of hydroxyl silicone oil, and grinding for 2.0h in a planetary ball mill to obtain expanded graphite loaded chlorinated paraffin;
(4) adding 20kg starch into a reactor, adding 30L water, stirring to obtain starch slurry, adding 5% Na
2CO
3Adjusting pH to 6.2-6.3, adding 3.0L CaCl with mass concentration of 5%
2Heating the solution to 93 ℃ under continuous stirring, adding 9.0g of liquefied α -amylase after the starch slurry is completely pasty, continuously stirring to liquefy the solution, and carrying out heat preservation reaction at 70-80 ℃ for 1.5h to obtain gelatinized starch;
(5) 40kg of gelatinized starch, 25kg of expanded perlite loaded mannitol-galactose, 13kg of expanded graphite loaded chlorinated paraffin, 10kg of light-burned magnesium oxide, 5.0kg of magnesium chloride, 12kg of melamine-phosphoric acid modified lignin, 2.5kg of polyoxyethylene ether oleate dustproof agent, 800g of organic silicon defoaming agent, 1.0kg of hydroxyl silicone oil and 0.8kg of amino silicone oil are added into a high-speed shearing stirrer, first shearing stirring is carried out for 4.0h at the rotating speed of 1500r/min, 10kg of waterborne polyurethane, 10kg of nano tin dioxide, 5.0kg of 400-mesh titanium dioxide, 5.0kg of 200-mesh sepiolite, 5.0kg of 200-mesh glass hollow floating bead, 5.0kg of 200-mesh kaolin, 5.0kg of 200-mesh mineral wool residue, 5.0kg of 2000-mesh ultrafine aluminum silicate and 120g of MONENG-1105 modified polydimethylsiloxane are added, second shearing stirring is carried out at the rotating speed of 2000r/min for 1.0h, and 200-mesh sieving is carried out, obtaining the water-based phase-change heat-absorbing expansion type flame-retardant tunnel flame-retardant fireproof coating.
Example 2:
the invention relates to a water-based phase-change heat-absorption intumescent flame-retardant fireproof coating for a tunnel, which comprises the following steps:
(1) heating 8.0kg of expanded perlite in a reactor to 80 ℃, simultaneously vacuumizing to 40kPa, preserving heat and vacuumizing for 20min, then adding 20kg of mannitol and 10kg of galactose which are molten under the protection of nitrogen, preserving heat and reacting at 80 ℃ for 60min under the protection of 2atm nitrogen, cooling the product to room temperature, adding 200g of hydroxyl silicone oil, and grinding in a planetary ball mill for 2.0h to obtain expanded perlite loaded with mannitol-galactose;
(2) adding 12kg of melamine and 2.0L of 0.5mol/L NaOH solution into a reaction kettle, uniformly stirring, slowly adding 8.0L of 37% formaldehyde while stirring, heating to 50 ℃, and carrying out a first stirring reflux reaction for 120min to obtain a melamine-formaldehyde prepolymer; 40kg of lignin was added to a reaction kettle, and 11kg of 85% H was added with stirring
3PO
4Stirring the solution, 10kg of urea and 2.0L of 3% hydrogen peroxide at 80 ℃ to perform dry type phosphorylation reaction for 3.5 hours; adding the melamine formaldehyde prepolymer under stirring, continuously stirring, heating to 80 ℃, and carrying out a second reflux reaction for 90min to obtain melamine-phosphoric acid modified lignin;
(3) heating 8.0kg of expanded graphite in a reactor to 80 ℃, simultaneously vacuumizing to 40kPa, preserving heat and vacuumizing for 20min, then adding 40kg of chlorinated paraffin cp42, preserving heat at normal pressure and 80 ℃, reacting for 60min, cooling a product to room temperature, adding 200g of hydroxyl silicone oil, and grinding for 2.0h in a planetary ball mill to obtain expanded graphite loaded chlorinated paraffin;
(4) adding 20kg starch into a reactor, adding 30L water, stirring to obtain starch slurry, adding 5% Na
2CO
3Adjusting pH to 6.2-6.3, adding 3.0L CaCl with mass concentration of 5%
2Heating the solution to 93 ℃ under continuous stirring, adding 9.0g of liquefied α -amylase after the starch slurry is completely pasty, continuously stirring to liquefy the solution, and carrying out heat preservation reaction at 70-80 ℃ for 1.5h to obtain gelatinized starch;
(5) 40kg of gelatinized starch, 20kg of expanded perlite loaded mannitol-galactose, 13kg of expanded graphite loaded chlorinated paraffin, 10kg of light-burned magnesium oxide, 5.0kg of magnesium chloride, 10kg of melamine-phosphoric acid modified lignin, 2.5kg of polyoxyethylene ether oleate dustproof agent, 800g of organic silicon defoaming agent, 1.0kg of hydroxyl silicone oil and 800g of amino silicone oil are added into a high-speed shearing stirrer, first shearing stirring is carried out for 4.0h at the rotating speed of 1500r/min, 10kg of waterborne polyurethane, 10kg of nano tin dioxide, 5.0kg of 400-mesh titanium dioxide, 5.0kg of 200-mesh sepiolite, 5.0kg of 200-mesh glass hollow floating bead, 5.0kg of 200-mesh kaolin, 5.0kg of 200-mesh slag cotton, 5.0kg of 2000-mesh ultrafine aluminum silicate and 120g of MONENG-1105 modified polydimethylsiloxane leveling agent are added, second shearing stirring is carried out for 1.0h at the rotating speed of 2000r/min, and 200-mesh sieving is carried out, obtaining the water-based phase-change heat-absorbing expansion type flame-retardant tunnel flame-retardant fireproof coating.
Example 3:
the invention relates to a water-based phase-change heat-absorption intumescent flame-retardant fireproof coating for a tunnel, which comprises the following steps:
(1) heating 8.0kg of expanded perlite in a reactor to 80 ℃, simultaneously vacuumizing to 40kPa, preserving heat and vacuumizing for 20min, then adding 20kg of mannitol and 10kg of galactose which are molten under the protection of nitrogen, preserving heat and reacting at 80 ℃ for 60min under the protection of 2atm nitrogen, cooling the product to room temperature, adding 200g of hydroxyl silicone oil, and grinding in a planetary ball mill for 2.0h to obtain expanded perlite loaded with mannitol-galactose;
(2) adding 12kg of melamine and 2.0L of 0.5mol/L NaOH solution into a reaction kettle, uniformly stirring, slowly adding 8.0L of 37% formaldehyde while stirring, heating to 50 ℃, stirring, and carrying out a first reflux reaction for 120min to obtain a melamine-formaldehyde prepolymer; 40kg of lignin was added to a reaction kettle, and 11kg of 85% H was added with stirring
3PO
4Stirring the solution, 10kg of urea and 2.0L of 3% hydrogen peroxide at 80 ℃ to perform dry type phosphorylation reaction for 3.5 hours; adding the melamine formaldehyde prepolymer under stirring, continuously stirring, heating to 80 ℃, and carrying out a second reflux reaction for 90min to obtain melamine-phosphoric acid modified lignin;
(3) heating 8.0kg of expanded graphite in a reactor to 80 ℃, simultaneously vacuumizing to 40kPa, preserving heat and vacuumizing for 20min, then adding 40kg of chlorinated paraffin cp42, preserving heat at normal pressure and 80 ℃, reacting for 60min, cooling a product to room temperature, adding 200g of hydroxyl silicone oil, and grinding for 2.0h in a planetary ball mill to obtain expanded graphite loaded chlorinated paraffin;
(4) adding 20kg starch into a reactor, adding 30L water, stirring to obtain starch slurry, adding 5% Na
2CO
3Adjusting pH to 6.2-6.3, adding 3.0L5% of CaCl
2Heating the solution to 93 ℃ under continuous stirring, adding 9.0g of liquefied α -amylase after the starch slurry is completely pasty, continuously stirring to liquefy the solution, and carrying out heat preservation reaction at 70-80 ℃ for 1.5h to obtain gelatinized starch;
(5) 40kg of gelatinized starch, 20kg of expanded perlite loaded mannitol-galactose, 13kg of expanded graphite loaded chlorinated paraffin, 10kg of light-burned magnesium oxide, 5.0kg of magnesium chloride, 8.0kg of melamine-phosphoric acid modified lignin, 2.5kg of polyoxyethylene ether oleate dustproof agent, 0.8kg of organic silicon defoaming agent, 1.0kg of hydroxyl silicone oil and 800g of amino silicone oil are added into a high-speed shearing stirrer, first shearing stirring is carried out for 4.0h at the rotating speed of 1500r/min, 10kg of waterborne polyurethane, 10kg of nano tin dioxide, 5.0kg of 400-mesh titanium dioxide, 5.0kg of 200-mesh sepiolite, 5.0kg of 200-mesh glass hollow floating bead, 5.0kg of 200-mesh kaolin, 5.0kg of 200-mesh slag cotton, 5.0kg of 2000-mesh ultrafine aluminum silicate and 120g of MONENG-1105 modified polydimethylsiloxane, second shearing stirring is carried out continuously at the rotating speed of 2000r/min for 1.0h, and 200-mesh sieving is carried out, obtaining the water-based phase-change heat-absorbing expansion type flame-retardant tunnel flame-retardant fireproof coating.
Comparative example 1:
an intumescent flame-retardant fireproof coating for tunnels is prepared by stirring the following raw materials in parts by weight: 90kg of refractory cement, 45kg of AEC expanded cement, 30kg of polyvinyl acetate emulsion, 25kg of urea-formaldehyde resin, 7kg of aluminum hydroxide, 12kg of sepiolite, 7kg of perlite, 12kg of fly ash, 12kg of polypropylene short fiber, 12kg of carboxymethyl cellulose, 8kg of fatty alcohol-polyoxyethylene ether, 7kg of fly ash glass microsphere, 14kg of kaolin and 6kg of ammonium polyphosphate.
The tunnel flame-retardant fireproof coatings prepared in the above examples 1 to 3 and comparative examples were measured for average heat capacity at 25 to 800 ℃ on a differential scanning calorimeter; measuring the expansion times by using the flame of an alcohol blast burner; measuring the peak value pHHR of the heat release rate and the smoke yield on a cone calorimeter; the fire resistance time, the bonding strength and the compressive strength are determined according to GB 28375 and 2012 fire-retardant coating for concrete structures. The results of the specific testing of the test specimens are shown in Table 1.
Table 1: flame-retardant and fireproof performance index of water-based phase-change heat-absorption intumescent tunnel flame-retardant and fireproof coating
As can be seen from table 1, in the aqueous phase-change heat-absorbing intumescent flame-retardant tunnel flame-retardant fire-retardant coating prepared by the preparation method of the invention in examples 1, 2 and 3, compared with the intumescent tunnel flame-retardant fire-retardant coating obtained in comparative example 1, under the condition that the coating thickness is only 1/2 of the comparative example, the indexes such as average heat capacity, expansion ratio, fire-resistant limit time, bonding strength, compressive strength and the like are greatly increased, and the peak value of heat release rate and the smoke release amount are greatly reduced. The water-based phase-change heat-absorption intumescent flame-retardant tunnel flame-retardant fireproof coating prepared by integrating the technologies of ' phase-change heat-absorption flame suppression, ' expanded carbon layer heat insulation protection ' and the like has excellent flame-retardant and fireproof performance indexes, can realize efficient flame-retardant and fireproof, effectively prevents the temperature of a tunnel concrete structure from rising, avoids the reduction of the mechanical strength of the tunnel concrete structure, and ensures the safety of lives and properties of people.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. The water-based phase-change heat-absorbing intumescent flame-retardant fireproof coating for the tunnel is characterized by comprising the following raw materials in parts by mass: 20-30 parts of expanded perlite loaded mannitol-galactose, 5-15 parts of melamine-phosphoric acid modified lignin, 5-15 parts of expanded graphite loaded chlorinated paraffin, 35-55 parts of gelatinized starch, 5-15 parts of light-burned magnesium oxide, 3-8 parts of magnesium chloride, 2-4 parts of polyoxyethylene ether oleate dustproof agent, 0.1-1.0 part of organic silicon defoamer, 0.5-2.0 parts of hydroxyl silicone oil, 0.1-1.0 part of amino silicone oil, 5-15 parts of waterborne polyurethane, 5-25 parts of nano tin dioxide, 5-10 parts of titanium dioxide, 20-40 parts of filler, 5-10 parts of aluminum silicate and 0.10-0.15 part of polyether modified polydimethylsiloxane leveling agent; the filler comprises 5-10 parts of sepiolite, 5-10 parts of glass hollow floating beads, 5-10 parts of kaolin and 5-10 parts of slag wool by weight;
the expanded perlite loaded mannitol-galactose is obtained by reacting expanded perlite, mannitol, galactose and hydroxyl silicone oil, the melamine-phosphoric acid modified lignin is obtained by reacting melamine, a sodium hydroxide solution, formaldehyde, lignin, a phosphoric acid solution, urea and hydrogen peroxide, the expanded graphite loaded chlorinated paraffin is obtained by reacting expanded graphite, chlorinated paraffin 42 and the hydroxyl silicone oil, and the gelatinized starch is obtained by reacting starch, water and liquefied α -amylase.
2. The flame-retardant fireproof coating for tunnels according to claim 1, wherein the mass ratio of the expanded perlite to the mannitol to the galactose to the hydroxyl silicone oil is (10-20) to (30-40) to (10-20) to (0.1-1.0);
the mass ratio of the melamine to the sodium hydroxide solution to the formaldehyde to the lignin to the phosphoric acid solution to the urea to the hydrogen peroxide is (10-15): (1.5-2.5): 6-10): 40-60): 10-12): 0.5-15): 1-5, the concentration of the sodium hydroxide solution is 0.1-1.0mol/L, the mass concentration of the formaldehyde is 37%, the mass concentration of the phosphoric acid solution is 50-85%, and the mass concentration of the hydrogen peroxide is 3%;
the mass ratio of the expanded graphite to the chlorinated paraffin 42 to the hydroxyl silicone oil is (10-20) to (80-90) to (0.1-1.0);
the mass ratio of the starch to the water to the liquefied α -amylase is (10-15) to 20: 0.006.
3. A method for preparing the water-based phase-change heat-absorbing intumescent tunnel flame-retardant fireproof coating as claimed in claim 1 or 2, comprising the following steps:
(1) heating the expanded perlite, vacuumizing, adding mannitol and galactose which are melted under the protection of nitrogen, preserving heat under the protection of nitrogen for reaction, cooling the obtained product to room temperature, adding hydroxyl silicone oil, and grinding to obtain expanded perlite loaded mannitol-galactose;
(2) mixing and stirring melamine and a sodium hydroxide solution uniformly, adding formaldehyde while stirring, and heating to perform a first reflux reaction to obtain a melamine formaldehyde prepolymer; adding a phosphoric acid solution, urea and hydrogen peroxide into lignin while stirring, stirring to perform a phosphorylation reaction, adding the melamine formaldehyde prepolymer while stirring after the reaction is completed, and continuously stirring and heating to perform a second reflux reaction to obtain melamine-phosphoric acid modified lignin;
(3) heating the expanded graphite, vacuumizing, adding chlorinated paraffin 42, keeping the temperature at normal pressure for reaction, cooling the product to room temperature after the reaction is finished, adding hydroxyl silicone oil, and grinding to obtain expanded graphite loaded chlorinated paraffin;
(4) adding starch into water, stirring to obtain starch slurry, adjusting pH to weak acidity, adding CaCl
2Stirring and heating the solution, adding the liquefied α -amylase after the starch slurry is completely pasty, continuously stirring to liquefy the starch, and keeping the temperature to react to obtain gelatinized starch;
(5) mixing the expanded perlite loaded with mannitol-galactose obtained in the step (1), the melamine-phosphoric acid modified lignin obtained in the step (2), the expanded graphite loaded with chlorinated paraffin obtained in the step (3), the gelatinized starch obtained in the step (4), light-burned magnesium oxide, magnesium chloride, polyoxyethylene ether oleate dustproof agent, organic silicon defoamer, hydroxyl silicone oil and amino silicone oil, performing first shearing and stirring, adding waterborne polyurethane, nano tin dioxide, titanium dioxide, sepiolite, glass hollow floating beads, kaolin, slag wool, aluminum silicate and modified polydimethylsiloxane leveling agent, continuing to perform second shearing and stirring, and sieving with a 200-mesh sieve to obtain the waterborne phase-change heat absorption expanded tunnel flame-retardant fireproof coating.
4. The preparation method according to the claim 3, wherein in the step (1), the heating temperature of the expanded perlite is 70-90 ℃, the vacuumizing is carried out for 20-50kPa, the vacuumizing time is 10-30min, the pressure of nitrogen is 2atm, the heat preservation temperature is 70-90 ℃, the heat preservation time is 40-80min, and the grinding time is 1.0-3.0 h.
5. The method as claimed in claim 3, wherein in the step (2), the heating temperature of the first reflux reaction is 40-60 ℃, and the reaction time is 110-130 min; the temperature of the phosphorylation reaction is 70-90 ℃, and the reaction time is 1-5 h; the temperature of the second reflux reaction is 70-90 ℃, and the reaction time is 80-100 min.
6. The preparation method according to claim 3, wherein in the step (3), the heating temperature of the expanded graphite is 70-90 ℃, the vacuumizing is carried out to reach 20-50kPa, the vacuumizing time is 10-30min, the temperature of the normal pressure heat preservation is 70-90 ℃, the reaction time is 40-80min, and the grinding time is 1.0-3.0 h.
7. The production method according to claim 3, wherein in the step (4), Na is used in a mass concentration of 5%
2CO
3Adjusting pH to 6.2-6.3 with CaCl
2The mass concentration of the solution is 5 percent, the stirring and heating temperature is 90-95 ℃, the heat preservation temperature is 70-80 ℃, and the reaction time is 0.5-2 h.
8. The production method according to any one of claims 3 to 7, wherein in the step (5), the fineness of titanium dioxide is 400 mesh, the fineness of sepiolite, glass hollow cenospheres, kaolin and slag wool are each 200 mesh, and the fineness of aluminum silicate is 2000 mesh.
9. The method as claimed in any one of claims 3 to 7, wherein in step (5), the rotation speed of the first and second shear stirring is 500-2000r/min, the time of the first shear stirring is 1.0-8.0h, and the time of the second shear stirring is 0.2-1.0 h.
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| CN113956777B (en) * | 2021-12-06 | 2022-12-13 | 烟台大学 | Preparation and application methods of self-repairing flame-retardant, droplet-resistant and abrasion-resistant polyurethane coating |
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