Phenolic aldehyde insulation board refractory material and production process thereof

Abstract

The invention discloses a phenolic aldehyde insulation board refractory material and a production process thereof. The material is prepared from the following raw materials in parts by weight: 100-150 parts of phenolic resin, 30-80 parts of inorganic fire-resistant filler, aluminum hydroxide, expanded vermiculite, wollastonite and calcium aluminate, 5-15 parts of curing agent and the like, 3-5% of montmorillonite nanosheets are intercalated in the phenolic resin, and a foaming agent is compounded according to a specific proportion. The production process comprises multiple steps of raw material pretreatment, phenolic resin modification and the like, and parameters are strictly controlled. By constructing a three-dimensional fireproof structure of'surface compact carbon layer-middle heat insulation bubbles-inner layer ceramic framework ', the fire endurance is greatly improved to 4.2 hours from 1.5 hours of a common plate, the high-temperature (800 DEG C) shrinkage rate is only 5%, and the stability and fireproof capability of the material at high temperature are effectively improved. Due to the unique fireproof structural design, a multi-layer protective barrier can be formed when a fire disaster occurs, heat and flame are effectively prevented from spreading, and more time is won for personnel evacuation and fire rescue.

Description

Technical Field

[0001] The invention relates to the technical field of thermal insulation materials, in particular to a phenolic thermal insulation board refractory material and a production process. Background Art

[0002] With the continuous improvement of building energy conservation and fire safety requirements, the performance of thermal insulation materials is also facing higher challenges. Phenolic insulation board has been widely used in the field of building insulation due to its excellent thermal insulation performance, low smoke and non-toxicity.

[0003] However, the existing phenolic insulation board still has certain deficiencies in fire resistance, such as easy decomposition and deformation at high temperature, resulting in reduced insulation and fireproof effects. At the same time, the traditional production process has problems such as low production efficiency and unstable product quality, which limits the further development and application of phenolic insulation board.

[0004] Therefore, it is necessary to provide a phenolic insulation board refractory material and a production process to solve the above technical problems. Summary of the invention

[0005] The purpose of the present invention is to provide a phenolic insulation board refractory material and a production process to solve the problems of low fire resistance limit, poor thermal insulation performance, insufficient mechanical properties, poor flame retardant performance, and poor material stability and uniformity of ordinary phenolic insulation boards.

[0006] To achieve the above object, the present invention provides the following technical solutions: In a first aspect, the present invention provides a phenolic insulation board refractory material, which comprises the following raw materials by weight: 100-150 parts of phenolic resin, 30-80 parts of inorganic refractory filler, 5-15 parts of curing agent, 1-5 parts of surfactant, 10-30 parts of flame retardant, 4-6 parts of fiber, 3-8 parts of catalyst, 2-16 parts of modifier, 5-7 parts of foaming agent, 5-15 parts of rubber particles, and 3-10 parts of graphite powder; the inorganic refractory filler comprises: 40-60 parts of aluminum hydroxide, 20-40 parts of expanded vermiculite, 5-15 parts of wollastonite, and 5-15 parts of calcium aluminate; the foaming agent is azodicarbonamide (ADCA) and sodium bicarbonate (NaHCO 3 ) with a mass ratio of 7:3; 3-5% of montmorillonite (MMT) nanosheets are inserted into the phenolic resin.

[0007] Preferably, the particle sizes of wollastonite and calcium aluminate are both 100-200 mesh.

[0008] Preferably, the interlayer spacing of the montmorillonite nanosheets is expanded to 2.5-3.0 nm by modification with an organic quaternary ammonium salt.

[0009] Preferably, the flame retardant comprises a compound of a phosphorus-based flame retardant, a nitrogen-based flame retardant and a silicon-based flame retardant.

[0010] Preferably, the catalyst is at least one of oxalic acid and p-toluenesulfonic acid.

[0011] Preferably, the modifier is at least one of polyvinyl alcohol and melamine.

[0012] In a second aspect, the present invention provides a production process of a phenolic insulation board refractory material, comprising the following steps: (1) Raw material pretreatment The inorganic refractory filler is crushed and sieved to make the particle size of aluminum hydroxide in the range of 80-150 meshes and the particle size of expanded vermiculite in the range of 100-200 meshes. At the same time, wollastonite and calcium aluminate are crushed and sieved to a particle size of 100-200 meshes. The two are used as ceramic precursors and will react at high temperature to generate ceramic phases such as mullite; rubber particles are screened to obtain rubber particles with a particle size of 0.5-2 mm, and the rubber particles are premixed with the inorganic refractory filler to form an inorganic refractory material premix; graphite powder is mixed with a polycarboxylate dispersant, the amount of the dispersant is 1%-3% of the mass of the graphite powder, and ultrasonic dispersion treatment is performed for 10-15 minutes; (2) Phenolic resin modification First, add phenolic resin into the reactor, start stirring and raise the temperature to 60-80°C, add catalyst and modifier into the phenolic resin, control the stirring speed at 80-120r / min, and react for 1-3h; 3-5% montmorillonite (MMT) nanosheets are intercalated into the phenolic resin, and the montmorillonite nanosheets begin to be preliminarily dispersed in the phenolic resin; (3) Adding inorganic refractory fillers The inorganic refractory material premix obtained in step (1) is added to the phenolic resin modified in step (2), and the stirring speed is maintained at 60 to 100 r / min for 15 to 20 minutes; wollastonite and calcium aluminate are preliminarily mixed with the phenolic resin and the montmorillonite nanosheets therein during the stirring process; (4) Adding additives In the reactor, surfactant and flame retardant are added in sequence, stirred at a speed of 120-150 r / min for 15-20 minutes, and then curing agent is added, and stirring is continued for 10-15 minutes; phosphorus, nitrogen, silicon and other components in the flame retardant begin to interact with phenolic resin, montmorillonite nanosheets and ceramic precursors (wollastonite and calcium aluminate); (5) Add graphite powder Add the graphite powder pretreated in step (1) into the reactor, increase the stirring speed to 150-200 r / min, and stir for 20-25 min; (6) Adding fibers during foaming Add a foaming agent into the reaction kettle. While the foaming agent decomposes to generate gas to foam the phenolic resin, add the fiber evenly into the resin system and stir at a speed of 300 to 1000 r / min for a foaming time of 30 to 35 minutes.

[0013] Preferably, in step (1), when the rubber particles and the inorganic refractory filler are premixed, the stirring speed is 30 to 50 r / min, and the stirring time is extended to 20 to 30 min.

[0014] Preferably, in step (1), before the rubber particles are premixed with the inorganic refractory filler, the rubber particles are stirred with talc accounting for 5% to 8% by weight at 30 to 50 r / min for 15 to 20 minutes to be uniformly mixed.

[0015] Preferably, in step (6), the fibers are added within 1 to 5 minutes after the foaming agent starts to decompose, and the addition time lasts for 2 to 10 minutes.

[0016] Compared with the prior art, the present invention has the following beneficial effects: 1. The azodicarbonamide in the present invention decomposes at 160°C to form a dense carbon layer on the surface of the material, and sodium bicarbonate decomposes at 270°C to form an insulating bubble layer inside. The two work together with the ceramic precursors wollastonite and calcium aluminate to construct a three-dimensional fireproof structure of "surface dense carbon layer-intermediate insulating bubbles-inner ceramic skeleton". The fire resistance limit is greatly increased from 1.5 hours of ordinary boards to 4.2 hours, and the high temperature (800°C) shrinkage rate is only 5%, which effectively improves the stability and fireproof ability of the material at high temperatures. This unique fireproof structural design can form a multi-layer protective barrier when a fire occurs, effectively preventing the spread of heat and flames, and buying more time for personnel evacuation and fire rescue.

[0017] 2. The present invention combines aluminum hydroxide and expanded vermiculite in a specific ratio. When aluminum hydroxide decomposes at high temperature, it absorbs a large amount of heat and releases water vapor to dilute oxygen, effectively inhibiting combustion. The porous structure of expanded vermiculite can block heat transfer. The two work together to greatly improve the fire resistance. According to tests, the fire resistance limit can reach more than 3.5 hours, far exceeding the 1.5 hours of ordinary phenolic insulation boards, providing more sufficient safety protection time for buildings in the event of a fire.

[0018] 3. The present invention forms a uniform and fine porous structure by precisely controlling the foaming process and the timing of fiber addition, thereby reducing air convection and heat conduction. The added graphite powder optimizes thermal performance and evenly distributes heat. The final thermal conductivity is as low as 0.030W / (m・K), and the temperature fluctuation range of the building space within 24 hours is 2°C smaller than that of ordinary panels, reducing building energy consumption and creating a more comfortable and stable indoor temperature environment for users. The uniform and fine porous structure is like countless tiny insulation units, which effectively prevents the transfer of heat, and the addition of graphite powder further optimizes the heat conduction path inside the material, making the insulation effect even better.

[0019] 4. The montmorillonite nanosheets in the present invention form a barrier network in the phenolic resin, inhibiting the high-temperature decomposition and volatilization of the phenolic resin and reducing the generation of combustible gases. Working in conjunction with the double foaming agent and ceramic precursor, it enhances the density and stability of the carbon layer and improves the thermal insulation performance; working in conjunction with the flame retardant, it reduces the release of toxic gases such as CO by 45%, enhances the smoke and toxicity suppression effects, and reduces fire hazards. The barrier effect of the montmorillonite nanosheets and the synergistic effect of the flame retardant inhibit the occurrence and development of combustion from multiple aspects, not only reducing the release of toxic gases, but also reducing the spread of smoke and flames, greatly improving the flame retardant safety of the material.

[0020] 5. The present invention adopts phosphorus, nitrogen, silicon and other flame retardants, and the action mechanisms of different flame retardants are complementary. The phosphorus system carbonizes the phenolic resin to form an insulation layer, the nitrogen system decomposes to produce non-combustible gas to dilute oxygen, and the silicon system forms a protective film on the surface. Under the synergistic effect, the smoke production is reduced by 30% compared with ordinary boards, and the flame propagation rate is reduced by 40%, which reduces the hazards when a fire occurs and buys more time for personnel evacuation and rescue. Moreover, phosphorus, nitrogen, silicon and other flame retardants are compounded, and the action mechanisms are complementary. The phosphorus system carbonizes the phenolic resin to form an insulation layer, the nitrogen system decomposes to produce non-combustible gas to dilute oxygen, and the silicon system forms a protective film on the surface. In collaboration with the double foaming agent and the ceramic precursor, the flame propagation rate is reduced by 40% and the smoke production is reduced by 30%, which significantly improves the flame retardant properties of the material and provides more reliable protection for building fire safety. DETAILED DESCRIPTION

[0021] The technical solution of the present invention will be clearly and completely described below in conjunction with specific embodiments. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention. Example

[0022] The present embodiment preferentially provides a phenolic insulation board refractory material, which includes the following raw materials by weight: 100-150 parts of phenolic resin, 30-80 parts of inorganic refractory filler, 5-15 parts of curing agent, 1-5 parts of surfactant, 10-30 parts of flame retardant, 4-6 parts of fiber, 3-8 parts of catalyst, 2-16 parts of modifier, 5-7 parts of foaming agent, 5-15 parts of rubber particles, and 3-10 parts of graphite powder; the inorganic refractory filler includes: 40-60 parts of aluminum hydroxide, 20-40 parts of expanded vermiculite, 5-15 parts of wollastonite, and 5-15 parts of calcium aluminate; the foaming agent is azodicarbonamide (ADCA) and sodium bicarbonate (NaHCO 3 ) with a mass ratio of 7:3; 3-5% of montmorillonite (MMT) nanosheets are inserted into the phenolic resin.

[0023] In this embodiment, azodicarbonamide decomposes at 160°C to produce gas, causing a dense carbon layer to begin to form on the surface of the material, blocking oxygen and heat transfer; as the temperature rises to 270°C, sodium bicarbonate decomposes to produce gas, forming an insulating bubble layer inside the material; azodicarbonamide decomposes at 160°C and sodium bicarbonate decomposes at 270°C, and the two produce gas in a gradient, and cooperate with the ceramic precursor to construct a three-dimensional fireproof structure of "surface dense carbon layer-intermediate insulating bubbles-inner ceramic skeleton"; at the same time, montmorillonite nanosheets inhibit the high-temperature decomposition and volatilization of phenolic resin, enhance the density and stability of the carbon layer, and react with ceramic precursors (wollastonite and calcium aluminate) at high temperature to promote the formation of ceramic phase; the flame retardant cooperates with the double foaming agent and ceramic precursor to flame retard, and cooperates with montmorillonite to reduce heat release and toxic gas generation.

[0024] More specifically, the particle sizes of wollastonite and calcium aluminate are both 100-200 meshes, and the particle size of graphite powder is 200-500 meshes.

[0025] More specifically, the flame retardant is a combination of one or more of a phosphorus-based flame retardant, a nitrogen-based flame retardant, and a silicon-based flame retardant.

[0026] In this embodiment, the flame retardant is selected from one or more of phosphorus, nitrogen, and silicon flame retardants. Different types of flame retardants have different mechanisms of action, and can produce synergistic effects when used in combination. For example, phosphorus flame retardants will form substances with strong dehydration effects such as phosphoric acid and metaphosphoric acid during combustion, carbonize phenolic resin, and form a carbonaceous layer that isolates oxygen and heat; nitrogen flame retardants are decomposed by heat to produce non-combustible gases, such as nitrogen, ammonia, etc., which dilute the concentration of combustible gases and oxygen; silicon flame retardants can form a siloxane protective film on the surface of the material to improve the thermal stability and oxidation resistance of the material. By rationally compounding these flame retardants, the flame retardant properties of the material can be accurately controlled according to actual needs, so that the fire safety of the phenolic insulation board is greatly improved, and the risk of fire is effectively reduced. According to tests, the smoke production of the phenolic insulation board of the present invention during combustion is reduced by 30% compared with ordinary phenolic insulation boards, and the flame propagation rate is reduced by 40%.

[0027] More specifically, the interlayer distance of the montmorillonite nanosheets is expanded to 2.5-3.0 nm by modification with organic quaternary ammonium salt.

[0028] In this embodiment, the modification process of montmorillonite nanosheets is as follows: select high-purity sodium montmorillonite, adapt to organic quaternary ammonium salt (such as CTAB), prepare deionized water, organic solvent and acid-base reagent. Add water to the original soil, stir and disperse, centrifuge to remove impurities, wash with water until there are no impurity ions, and dry at 60-80°C. Prepare the organic quaternary ammonium salt solution, add purified montmorillonite, stir and react at 50-80°C and 300-600r / min for 6-12 hours, and adjust the pH to 7-9 as needed. The product is centrifuged, the solvent or water is washed to remove impurities, and the product is dried at 60-80°C and then ground and sieved. Use XRD to calculate the interlayer spacing, TEM to observe the morphology and structure, and FT-IR to test the functional group changes to confirm the modification effect.

[0029] More specifically, the fiber is at least one of glass fiber, basalt fiber and carbon fiber, and the fiber diameter is 5 to 20 μm and the length is 3 to 15 mm.

[0030] In the present embodiment, at least one of glass fiber, basalt fiber and carbon fiber is selected as reinforcing fiber, and the fiber diameter is 5-20 μm and the length is 3-15 mm. These fibers have the characteristics of high strength and high modulus, are evenly distributed in the phenolic resin matrix, can effectively bear external loads, and improve the tensile, compressive and flexural strength of the material. In the foaming process, by accurately controlling the addition time and stirring speed of the fiber, the fiber is fully combined with the phenolic resin to form a firm reinforcement system. Through mechanical property test, the compressive strength of the phenolic insulation board of the present invention can reach 0.8MPa, and the flexural strength can reach 0.4MPa, which is significantly improved compared with the compressive strength 0.5MPa and flexural strength 0.2MPa of the common phenolic insulation board, so that it is less prone to damage during transportation and construction, and can better meet the needs of practical engineering applications. In the impact test during simulated transportation and construction, the breakage rate of the phenolic insulation board of the present invention is reduced by 40% compared with the common phenolic insulation board.

[0031] More specifically, the catalyst is at least one of oxalic acid and p-toluenesulfonic acid.

[0032] More specifically, the modifier is at least one of polyvinyl alcohol and melamine.

[0033] This embodiment also provides a production process of a phenolic insulation board refractory material, comprising the following steps: (1) Raw material pretreatment The inorganic refractory filler is crushed and sieved to make the particle size of aluminum hydroxide in the range of 80-150 meshes and the particle size of expanded vermiculite in the range of 100-200 meshes. At the same time, wollastonite and calcium aluminate are crushed and sieved to a particle size of 100-200 meshes. The two are used as ceramic precursors and will react at high temperature to generate ceramic phases such as mullite; rubber particles are screened to obtain rubber particles with a particle size of 0.5-2 mm, and the rubber particles are premixed with the inorganic refractory filler to form an inorganic refractory material premix; graphite powder is mixed with a polycarboxylate dispersant, the amount of the dispersant is 1%-3% of the mass of the graphite powder, and ultrasonic dispersion treatment is performed for 10-15 minutes; In this step, this embodiment uses aluminum hydroxide, expanded vermiculite, wollastonite, and calcium aluminate as inorganic refractory fillers, and combines them in a specific ratio (40-60 parts of aluminum hydroxide, 20-40 parts of expanded vermiculite, 5-15 parts of wollastonite, and 5-15 parts of calcium aluminate), which plays a good synergistic fire-resistant effect. Aluminum hydroxide will undergo an endothermic decomposition reaction at high temperatures, absorbing a large amount of heat, thereby reducing the surface temperature of the material and delaying the combustion process of the material. At the same time, the water vapor produced by its decomposition can dilute the surrounding oxygen concentration and further inhibit combustion. Expanded vermiculite has a porous structure, which can not only block heat transfer, but also has good structural stability at high temperatures, which can effectively enhance the fire resistance of the material. The two cooperate with each other, so that the fire resistance limit of the phenolic insulation board is greatly improved compared with that of ordinary phenolic insulation boards. After testing, under standard fire resistance test conditions, the fire resistance limit of the phenolic insulation board of the present invention can reach more than 3.5h, while the fire resistance limit of ordinary phenolic insulation boards is usually only 1.5h.

[0034] At the same time, the inorganic refractory filler is crushed and screened to make the aluminum hydroxide particle size 80-150 mesh and the expanded vermiculite particle size 100-200 mesh, ensuring that the filler particles are uniform in size and can be more evenly dispersed in the phenolic resin system during the subsequent mixing process. Wollastonite and calcium aluminate are crushed and screened to a particle size of 100-200 mesh. The two are used as ceramic precursors and will react at high temperatures to generate ceramic phases such as mullite. The rubber particles are screened to obtain particles with a particle size of 0.5-2mm, and a series of pretreatment and mixing operations are performed to ensure their uniform distribution in the material. Graphite powder is mixed with a polycarboxylate dispersant and ultrasonically dispersed for 10-15min, which effectively prevents the agglomeration of graphite powder and enables it to be evenly dispersed in the system, laying the foundation for the stability and uniformity of material performance. Scanning electron microscopy (SEM) observations show that the dispersion uniformity of each raw material in the phenolic insulation board of the present invention is 35% higher than that of ordinary phenolic insulation boards.

[0035] (2) Phenolic resin modification First, add phenolic resin into the reactor, start stirring and raise the temperature to 60-80°C, add catalyst and modifier into the phenolic resin, control the stirring speed at 80-120r / min, and react for 1-3h; 3-5% montmorillonite (MMT) nanosheets are intercalated into the phenolic resin, and the montmorillonite nanosheets begin to be preliminarily dispersed in the phenolic resin; In this step, the MMT nanosheet forms a barrier network in the phenolic resin, which can inhibit the decomposition and volatilization of the phenolic resin at high temperatures and reduce the generation of combustible gases. At the same time, it synergizes with the fireproof structure formed by the double foaming agent to further enhance the density and stability of the carbon layer and improve the thermal insulation performance of the material. At high temperatures, MMT can also react with ceramic precursors to promote the formation of ceramic phases and enhance the strength and integrity of the inner ceramic skeleton. The MMT nanosheet has a barrier effect and can reduce the release of toxic gases such as CO, reducing the release of CO by 45%. At the same time, the mullite generated by the reaction of silicon-based flame retardants with calcium aluminate can also inhibit the diffusion of toxic gases. MMT and flame retardants work synergistically to further enhance the smoke and toxicity suppression effects of the material and reduce the hazards when a fire occurs.

[0036] (3) Adding inorganic refractory fillers The inorganic refractory material premix obtained in step (1) is added to the phenolic resin modified in step (2), and the stirring speed is maintained at 60 to 100 r / min for 15 to 20 minutes; wollastonite and calcium aluminate are preliminarily mixed with the phenolic resin and the montmorillonite nanosheets therein during the stirring process; (4) Adding additives In the reactor, surfactant and flame retardant are added in sequence, stirred at a speed of 120-150 r / min for 15-20 minutes, and then curing agent is added, and stirring is continued for 10-15 minutes; phosphorus, nitrogen, silicon and other components in the flame retardant begin to interact with phenolic resin, montmorillonite nanosheets and ceramic precursors (wollastonite and calcium aluminate); In the above steps of this embodiment, in the process of phenolic resin modification, the reaction temperature (60-80°C), stirring speed (80-120r / min) and reaction time (1-3h) are precisely controlled to ensure that the modification reaction is sufficient and stable. In the process of adding each raw material and auxiliary agent, the stirring speed and time are strictly controlled, such as when adding inorganic refractory filler, the stirring speed is maintained at 60-100r / min, and stirring is 15-20min; when adding auxiliary agents, stirring is carried out at a specific speed and time in turn. These strict process controls ensure that each raw material is fully mixed in the phenolic resin system and the reaction is carried out evenly, so that the prepared phenolic insulation board has good stability and uniformity in performance, and the performance difference between different batches of products is extremely small, which can meet the requirements of large-scale production and engineering application for product quality consistency. Performance testing was carried out on 10 batches of products produced continuously. The coefficient of variation of each performance index of the phenolic insulation board of the present invention was controlled within 5%, while the coefficient of variation of ordinary phenolic insulation board was usually around 15%.

[0037] (5) Add graphite powder Add the graphite powder pretreated in step (1) into the reactor, increase the stirring speed to 150-200 r / min, and stir for 20-25 min; In this step, the present embodiment adds 3-10 parts of graphite powder with a particle size of 200-500 mesh. The graphite powder has good thermal conductivity and can form a heat conduction channel inside the material to evenly distribute the heat and avoid local heat accumulation. At the same time, the presence of graphite powder does not destroy the thermal insulation structure of the entire material, but optimizes the thermal performance of the material to a certain extent, further improving the thermal insulation effect of the thermal insulation board. It is found through thermal imaging that the uniformity of the wall surface temperature distribution of the phenolic thermal insulation board using the present invention is 25% higher than that of the ordinary phenolic thermal insulation board.

[0038] (6) Adding fibers during foaming Add a foaming agent into the reaction kettle. While the foaming agent decomposes to generate gas to foam the phenolic resin, add the fiber evenly into the resin system and stir at a speed of 300 to 1000 r / min for a foaming time of 30 to 35 minutes.

[0039] In this step of the present embodiment, the foaming agent (5-7 parts) decomposes in the phenolic resin system to produce gas, so that the phenolic resin is foamed to form a porous structure. During the foaming process, the foaming time (30-35min) and the stirring speed (300-1000r / min), as well as the timing and time of fiber addition (addition starts within 1-5min after the foaming agent begins to decompose, and the addition time lasts for 2-10min) are precisely controlled to ensure that the pores are uniform and fine. This uniform and fine porous structure greatly reduces air convection and heat conduction, thereby effectively improving the thermal insulation performance of the material. According to testing, the thermal conductivity of the phenolic insulation board of the present invention can be as low as 0.030W / (m・K), which is much lower than the thermal conductivity of ordinary phenolic insulation board 0.045W / (m・K), and the thermal insulation effect is significantly better than similar products. Under the same thermal insulation environment, the temperature fluctuation range of the building space using the phenolic insulation board of the present invention within 24 hours is reduced by 2°C compared with the building space using ordinary phenolic insulation board.

[0040] More specifically, in step (1), when the rubber particles and the inorganic refractory filler are premixed, the stirring speed is 30 to 50 r / min, and the stirring time is extended to 20 to 30 min.

[0041] More specifically, in step (1), before the rubber particles are premixed with the inorganic refractory filler, the rubber particles and talc accounting for 5% to 8% by weight of the rubber particles are stirred at 30 to 50 r / min for 15 to 20 minutes to be uniformly mixed.

[0042] More specifically, in step (6), the fibers are added within 1 to 5 minutes after the foaming agent starts to decompose, and the addition time lasts for 2 to 10 minutes.

[0043] In this step of the present embodiment, the buffer material adopts rubber particles (5-15 parts). The rubber particles have good flexibility and elasticity, can absorb and disperse external impact force, and improve the toughness of the material. Before premixing with the inorganic refractory filler, the rubber particles are stirred at 30-50r / min for 15-20min with talcum powder accounting for 5%-8% of its mass. The talcum powder can improve the surface properties of the rubber particles and enhance its bonding with other raw materials. During the premixing process, the stirring speed is controlled at 30-50r / min, and the stirring time is extended to 20-30min, so that the rubber particles are evenly distributed in the inorganic refractory filler. This synergistic effect makes the phenolic insulation board have good toughness while having high strength, and improves the comprehensive mechanical properties of the material. Through the drop hammer impact test test, the phenolic insulation board of the present invention can withstand 10J of impact energy without breaking, which is greatly improved compared with the 5J of the ordinary phenolic insulation board.

[0044] Comparative Example 1: The only difference between Comparative Example 1 and Example 1 is that only a single foaming agent is used, and there is no synergistic effect of the dual foaming agent and the ceramic precursor.

[0045] Raw material formula: 120 parts of phenolic resin, 50 parts of inorganic refractory filler (40 parts of aluminum hydroxide, 10 parts of expanded vermiculite, excluding wollastonite and calcium aluminate), 10 parts of curing agent, 3 parts of surfactant, 15 parts of flame retardant (phosphorus, nitrogen and silicon are compounded according to the invention ratio), 5 parts of fiber (mixed according to the invention fiber type and ratio), 5 parts of catalyst (mixed according to the invention type and ratio), 10 parts of modifier (mixed according to the invention type and ratio), 6 parts of foaming agent (only single azodicarbonamide), 10 parts of rubber particles, 5 parts of graphite powder, 3% montmorillonite (MMT) nanosheets intercalated in phenolic resin Production process: After the inorganic refractory filler is crushed and screened, the particle size of aluminum hydroxide is 80-150 meshes, and the particle size of expanded vermiculite is 100-200 meshes.

[0046] When the rubber particles and the inorganic refractory filler are premixed, the stirring speed is 30-50r / min and the stirring time is 20-30min.

[0047] When modifying phenolic resin, the temperature is controlled at 60-80°C, the stirring speed is 80-120r / min, and the reaction time is 1-3h.

[0048] When adding additives, add surfactant and flame retardant in sequence, stir at a speed of 120-150r / min for 15-20min, then add curing agent and continue stirring for 10-15min.

[0049] When adding graphite powder, the stirring speed is 150-200r / min and the stirring time is 20-25min.

[0050] During the foaming process, the foaming time is 30-35 minutes, the stirring speed is 300-1000r / min, and the fiber begins to be added within 1-5 minutes after the foaming agent begins to decompose, and the addition time lasts for 2-10 minutes.

[0051] Comparative Example 2: The only difference between Comparative Example 2 and Example 1 is that there is no nano-montmorillonite synergy.

[0052] Raw material formula: 120 parts of phenolic resin, 50 parts of inorganic refractory filler (40 parts of aluminum hydroxide, 10 parts of expanded vermiculite, 5 parts of wollastonite, 5 parts of calcium aluminate), 10 parts of curing agent, 3 parts of surfactant, 15 parts of flame retardant (phosphorus, nitrogen and silicon are compounded according to the proportion of the invention), 5 parts of fiber (mixed according to the type and proportion of the fiber of the invention), 5 parts of catalyst (mixed according to the type and proportion of the invention), 10 parts of modifier (mixed according to the type and proportion of the invention), 6 parts of foaming agent (azodicarbonamide and sodium bicarbonate are compounded according to the proportion of the invention), 10 parts of rubber particles, 5 parts of graphite powder, and unintercalated montmorillonite (MMT) nanosheets in phenolic resin.

[0053] Production process: same as comparative example 1 Comparative Example 3: The only difference between Comparative Example 3 and Example 1 is that there is no flame retardant synergist.

[0054] Raw material formula: 120 parts of phenolic resin, 50 parts of inorganic refractory filler (40 parts of aluminum hydroxide, 10 parts of expanded vermiculite, 5 parts of wollastonite, 5 parts of calcium aluminate), 10 parts of curing agent, 3 parts of surfactant, 15 parts of flame retardant (only single phosphorus flame retardant), 5 parts of fiber (mixed according to the types and proportions of the invention), 5 parts of catalyst (mixed according to the types and proportions of the invention), 10 parts of modifier (mixed according to the types and proportions of the invention), 6 parts of foaming agent (azodicarbonamide and sodium bicarbonate are compounded according to the proportions of the invention), 10 parts of rubber particles, 5 parts of graphite powder, and 3% montmorillonite (MMT) nanosheets intercalated in the phenolic resin.

[0055] Production process: same as Comparative Example 1.

[0056] Experimental data comparison table: Experimental data analysis: Fire resistance and high temperature shrinkage: Comparative Example 1 lacks the synergy of double foaming agent and ceramic precursor, and cannot construct an effective three-dimensional fireproof structure. The fire resistance is only 3.0h, and the high temperature shrinkage is 10%. Although Comparative Example 2 has double foaming agent and ceramic precursor, it does not have the synergistic enhancement of nano-montmorillonite, and the fire resistance and high temperature shrinkage are not as good as Example 1. Comparative Example 3 has no flame retardant synergy, and the fire resistance performance is also poor.

[0057] CO emission: Comparative Example 2 has no nano-montmorillonite barrier, and the CO emission reduction ratio is only 20%, which is much lower than 45% of the embodiment. Comparative Examples 1 and 3 have poor CO emission reduction effects due to the lack of relevant synergy.

[0058] Flame propagation rate and smoke production: The single flame retardant in Comparative Example 3 cannot achieve mechanism complementarity, and the flame propagation rate and smoke production reduction ratios are not ideal. Comparative Examples 1 and 2 are also inferior to Example 1 in these two indicators due to the lack of their respective synergistic effects.

[0059] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the present invention can be implemented in other specific forms without departing from the spirit or essential features of the present invention. Therefore, the embodiments should be considered exemplary and non-restrictive in all respects, and the scope of the present invention is defined by the appended claims rather than the above description, and it is intended that all changes falling within the meaning and scope of the equivalent elements of the claims be included in the present invention.

Claims

1. A phenolic insulation board refractory material, characterized in that: The raw materials include, by weight: 100-150 parts of phenolic resin, 30-80 parts of inorganic refractory filler, 5-15 parts of curing agent, 1-5 parts of surfactant, 10-30 parts of flame retardant, 4-6 parts of fiber, 3-8 parts of catalyst, 2-16 parts of modifier, 5-7 parts of foaming agent, 5-15 parts of rubber particles, and 3-10 parts of graphite powder; The inorganic refractory filler comprises: 40-60 parts of aluminum hydroxide, 20-40 parts of expanded vermiculite, 5-15 parts of wollastonite, and 5-15 parts of calcium aluminate; The foaming agent is a compound of azodicarbonamide (ADCA) and sodium bicarbonate (NaHCO3), with a mass ratio of 7:3; 3-5% of montmorillonite (MMT) nanosheets are intercalated in the phenolic resin.

2. The phenolic insulation board refractory material according to claim 1, characterized in that: The particle sizes of the wollastonite and calcium aluminate are both 100-200 meshes.

3. The phenolic insulation board refractory material according to claim 1, characterized in that: The interlayer distance of the montmorillonite nanosheets is expanded to 2.5-3.0 nm by modification with organic quaternary ammonium salt.

4. The phenolic insulation board refractory material according to claim 1, characterized in that: The flame retardant comprises a compound of a phosphorus flame retardant, a nitrogen flame retardant and a silicon flame retardant.

5. The phenolic insulation board refractory material according to claim 1, characterized in that: The catalyst is at least one of oxalic acid and p-toluenesulfonic acid.

6. The phenolic insulation board refractory material according to claim 1, characterized in that: The modifier is at least one of polyvinyl alcohol and melamine.

7. A production process of a phenolic insulation board refractory material according to any one of claims 2 to 6, characterized in that: The following steps are involved: (1) Raw material pretreatment The inorganic refractory filler is crushed and sieved to make the particle size of aluminum hydroxide in the range of 80-150 meshes and the particle size of expanded vermiculite in the range of 100-200 meshes. At the same time, wollastonite and calcium aluminate are crushed and sieved to a particle size of 100-200 meshes. The two are used as ceramic precursors and will react at high temperature to generate ceramic phases such as mullite. The rubber particles are screened to obtain rubber particles with a particle size of 0.5 to 2 mm, and the rubber particles are premixed with an inorganic refractory filler to form an inorganic refractory material premix; Mix graphite powder with a polycarboxylate dispersant, the amount of the dispersant being 1% to 3% of the mass of the graphite powder, and perform ultrasonic dispersion treatment for 10 to 15 minutes; (2) Phenolic resin modification First, add phenolic resin into the reactor, start stirring and raise the temperature to 60-80°C, add catalyst and modifier into the phenolic resin, control the stirring speed at 80-120r / min, and react for 1-3h; 3-5% montmorillonite (MMT) nanosheets are intercalated into the phenolic resin, and the montmorillonite nanosheets begin to be preliminarily dispersed in the phenolic resin; (3) Adding inorganic refractory fillers The inorganic refractory material premix obtained in step (1) is added to the phenolic resin modified in step (2), and the stirring speed is maintained at 60 to 100 r / min for 15 to 20 minutes; wollastonite and calcium aluminate are preliminarily mixed with the phenolic resin and the montmorillonite nanosheets therein during the stirring process; (4) Adding additives In the reactor, surfactant and flame retardant are added in sequence, stirred at a speed of 120-150 r / min for 15-20 minutes, and then curing agent is added, and stirring is continued for 10-15 minutes; phosphorus, nitrogen, silicon and other components in the flame retardant begin to interact with phenolic resin, montmorillonite nanosheets and ceramic precursors (wollastonite and calcium aluminate); (5) Add graphite powder Add the graphite powder pretreated in step (1) into the reactor, increase the stirring speed to 150-200 r / min, and stir for 20-25 min; (6) Adding fibers during foaming Add a foaming agent into the reaction kettle. While the foaming agent decomposes to generate gas to foam the phenolic resin, add the fiber evenly into the resin system and stir at a speed of 300 to 1000 r / min for a foaming time of 30 to 35 minutes.

8. The production process of a phenolic insulation board refractory material according to claim 7, characterized in that: In step (1), when the rubber particles and the inorganic refractory filler are premixed, the stirring speed is 30 to 50 r / min, and the stirring time is extended to 20 to 30 min.

9. The production process of a phenolic insulation board refractory material according to claim 7, characterized in that: In step (1), before the rubber particles are premixed with the inorganic refractory filler, the rubber particles and talc accounting for 5% to 8% of the rubber particles by weight are stirred at 30 to 50 r / min for 15 to 20 minutes to be uniformly mixed.

10. The production process of a phenolic insulation board refractory material according to claim 7, characterized in that: In step (6), the fiber begins to be added within 1 to 5 minutes after the foaming agent begins to decompose, and the addition time lasts for 2 to 10 minutes.