A rock wool board prepared by utilizing fly ash from garbage incineration and a processing method thereof

Abstract

The present invention relates to the technical field of rock wool boards, and specifically to a rock wool board prepared using fly ash from garbage incineration and a processing method thereof. The present invention uses fly ash from garbage incineration, basalt, limestone, slag, clay, gypsum, glass fiber, and pebbles as raw materials, mixes and melts them, and then undergoes a fiberization treatment to obtain fiber filaments; the fiber filaments are mixed with epoxy resin glue, pressurized and heated to obtain a rock wool board; the present invention adds an epoxy-based silicon-containing flame retardant oligomer to the epoxy resin glue, and the epoxy-based silicon-containing flame retardant oligomer improves the heat resistance, flame retardancy, and compression strength of the epoxy resin. The rock wool board prepared by the present invention has good performance and realizes the resource utilization of fly ash from garbage incineration.

Description

Technical Field

[0001] The invention relates to the technical field of rock wool boards, and in particular to a rock wool board prepared by utilizing fly ash from garbage incineration and a processing method thereof. Background Art

[0002] Rock wool board is a kind of thermal insulation decorative board, which belongs to building materials. Rock wool board has many advantages such as light weight, low thermal conductivity, heat absorption, non-combustibility, etc. Therefore, its production process has high requirements for raw materials. The materials for traditional production of rock wool board mainly come from natural ores, and the mining cost of natural ores is high, the resources are limited and the price is expensive, which leads to the high price of rock wool board.

[0003] With the accelerated development of industrialization, the amount of solid waste is increasing day by day. As an important means of solid waste treatment, waste incineration can give priority to alleviating the problems caused by the growth of waste. However, the fly ash produced by incineration contains a large amount of harmful substances. If it is directly landfilled, it will not only occupy a large amount of land resources, but also have the risk of damaging the ecological environment, posing a serious threat to the survival of humans and other organisms. In recent years, the use of incineration fly ash as a raw material for the production of rock wool boards can not only achieve the secondary utilization of waste, but also reduce the production cost of rock wool boards. Traditional rock wool boards use phenolic resin as an adhesive. Phenolic resin has good heat resistance and high strength, but it will cause formaldehyde pollution. As people pay more attention to health, its indoor application is restricted. Epoxy resin is also a common adhesive, but its heat resistance is not as good as phenolic resin, and it is brittle. It is very necessary to modify it to address the above problems. Summary of the invention

[0004] The object of the present invention is to provide a rock wool board prepared by utilizing waste incineration fly ash and a processing method thereof, so as to solve the problems raised in the above-mentioned background technology.

[0005] In order to solve the above technical problems, the present invention provides the following technical solutions: a rock wool board prepared by using fly ash from garbage incineration and a processing method thereof, comprising the following steps:

[0006] Step 1:

[0007] S11: Collect fly ash from garbage incineration, sieve it with a sieve with an aperture of 3-5 mm to remove large particles, remove iron-based impurities by magnetic attraction, pickle it with a dilute hydrochloric acid solution with a mass concentration of 1-3%, and dry it for later use;

[0008] S12: grinding and sieving the treated waste incineration fly ash, basalt, limestone, slag, clay, gypsum, glass fiber and pebbles respectively to form a mixed material; melting the mixed material to obtain a molten liquid, introducing nitrogen for protection during the melting treatment, the melting treatment temperature is 1500-1600° C., and the melting treatment time is 2-3 hours; using a centrifugal flight method to fiberize the molten liquid to obtain fiber filaments;

[0009] Step 2:

[0010] S21: mixing epoxy resin E51, curing agent, defoaming agent and epoxy diluent, and adding epoxy-based silicon-containing flame retardant oligomer to obtain epoxy resin mixed glue;

[0011] S22: According to the weight percentage, 10-15% of epoxy resin mixed glue and 85-90% of fiber filaments are mixed, and then fed, compressed, heated and cured, and cooled to obtain the product.

[0012] Further, in S12, the treated waste incineration fly ash, basalt, limestone, slag, clay, gypsum, glass fiber, and pebbles are ground and sieved respectively to control the particle size to 80-120 μm; and are mixed according to a weight ratio of (57-60): (20-30): (5-10): (15-25): (5-8): (3-5): (1-3): (1-2); and fiber filaments with a length of 5-20 mm are obtained.

[0013] Furthermore, in S21, the contents of the components in the epoxy resin mixed adhesive are, by weight, 100 parts of epoxy resin E51, 45-52 parts of curing agent, 0.5-1 part of defoaming agent, and 5-8 parts of epoxy diluent; the total weight of the epoxy-based silicon-containing flame retardant oligomer is 8-12% of the total weight of the epoxy resin E51.

[0014] Further, in S21, the method for preparing the epoxy-based silicon-containing flame retardant oligomer comprises the following steps:

[0015] Step a. Disperse 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in tetrahydrofuran, control the system temperature to 8-12°C, drip acrylic acid with stirring, and continue stirring to react for 3-4 hours after the addition is complete. After the reaction is completed, rotary evaporate at 40-50°C and dry in a drying oven at a constant temperature to obtain monocarboxyphosphaphenanthrene;

[0016] Step b. Mix 2,4,6,8-tetramethylcyclotetrasiloxane and allyl glycidyl ether, heat to 50-60°C, stir for 5-10 minutes, add Custer catalyst, stir until the temperature stabilizes, and continue the reaction for 3-5 hours to obtain tetraepoxy-grafted siloxane;

[0017] Step c. dispersing tetraepoxy-grafted siloxane and monocarboxylphosphaphenanthrene in anhydrous toluene, adding a catalyst benzyltriethylammonium chloride, heating to 100-110° C. and reacting for 3-5 hours to obtain a phosphaphenanthrene-grafted organosilicon;

[0018] Step d. Melt magnolol at 160-170° C., add phosphaphenanthrene grafted silicone with stirring, react for 24-36 hours with butyltriphenylphosphonium bromide as a catalyst, wash with deionized water after cooling, and dry to obtain an epoxy-based silicon-containing flame retardant oligomer.

[0019] Furthermore, in step a, the molar ratio of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to acrylic acid is 1:1; in step b, 2,4,6,8-tetramethylcyclotetrasiloxane and allyl glycidyl ether are mixed in a molar ratio of 1:4; in step c, tetraepoxy-grafted siloxane and monocarboxyphosphaphenanthrene are reacted in a molar ratio of epoxy group to carboxyl group of 2:1; in step d, magnolol and phosphaphenanthrene-grafted silicone are reacted in a molar ratio of phenolic hydroxyl group to epoxy group of 1:2.

[0020] Further, in S22, 10-15% of epoxy resin mixed glue is mixed with 85-90% of fiber filaments by weight.

[0021] Furthermore, in S22, the compression pressure is 5~8MPa; the curing temperature is 150~180°C; and the curing time is 2~3h.

[0022] Compared with the prior art, the beneficial effects achieved by the present invention are as follows: the present invention provides a process for preparing rock wool board using fly ash from garbage incineration, turning waste fly ash into treasure and realizing resource utilization. The present invention uses fly ash from garbage incineration, basalt, limestone, slag, clay, gypsum, glass fiber, and pebbles as raw materials, mixes and melts them, and then undergoes fiberization treatment to obtain fiber filaments. The fiber filaments are mixed with epoxy resin, pressurized, and heated to obtain rock wool board.

[0023] Conventional epoxy resin materials are flammable and brittle after curing. Based on the above process, the present invention further modifies the epoxy resin and adds epoxy-containing silicon flame retardant oligomers. The preparation method of epoxy-containing silicon flame retardant oligomers is as follows: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide reacts with acrylic acid to obtain monocarboxyphosphaphenanthrene; 2,4,6,8-tetramethylcyclotetrasiloxane reacts with allyl glycidyl ether to obtain tetraepoxy-grafted siloxane; tetraepoxy-grafted siloxane and monocarboxyphosphaphenanthrene are subjected to esterification reaction at a molar ratio of epoxy group to carboxyl group of 2:1 to obtain phosphaphenanthrene-grafted silicone; the phosphaphenanthrene-grafted silicone contains two epoxy groups, which can react with the two phenolic hydroxyl groups on magnolol, and react at a molar ratio of phenolic hydroxyl group to epoxy group of 1:2 to obtain epoxy-containing silicon flame retardant oligomers. The epoxy-based silicon-containing flame-retardant oligomer contains two epoxy groups, which can react with the epoxy resin under the action of the curing agent and be introduced into the epoxy resin through chemical bonds; the siloxane in the oligomer has good toughness, and the magnolia biphenyl structure improves the rigidity of the epoxy resin. The combination of the two improves the strength of the epoxy resin while increasing its flexibility, and jointly improves the mechanical properties of the resin; after introducing magnolia into the epoxy resin, the cross-linking density becomes larger and the heat resistance is stronger. It synergistically improves the heat resistance of the epoxy resin with siloxane, slows down the thermal weight loss process, and has a high residual carbon rate during the combustion process, thereby showing good flame retardant properties.

[0024] During the experiment, the researchers found that due to the grafting of multiple 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxides in the epoxy-based silicon-containing flame retardant oligomer, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide not only gives the material flame retardant properties, but also has a large steric hindrance. If the dosage is too high, it will affect the thermal curing of the epoxy resin. After repeated experiments, it was found that when the weight of the epoxy-based silicon-containing flame retardant oligomer is 8-12% of the total weight of the epoxy resin, the obtained rock wool board has good heat resistance, flame retardancy and compressive strength. DETAILED DESCRIPTION

[0025] Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative work shall fall within the scope of protection of the present invention.

[0026] Materials and sources used in the present invention: waste incineration fly ash comes from Zhongjielan Environmental Protection Technology Co., Ltd.; basalt comes from Hubei Jiuhua Basalt Co., Ltd.; limestone comes from Shandong CITIC Calcium Industry Co., Ltd.; slag comes from Jiangsu Rongda New Materials Co., Ltd.; clay comes from Zhejiang Fenghong New Materials Co., Ltd.; gypsum comes from Taishan Gypsum Co., Ltd.; glass fiber comes from China Jushi Co., Ltd.; pebbles come from Nanjing Dacheng Landscape Engineering Co., Ltd.; epoxy resin E51 comes from Hebei Linyuan Fine Chemical Co., Ltd.; curing agent is 4,4'-diaminodiphenyl sulfone, from Aladdin Biochemical Technology Co., Ltd.; defoamer comes from Foshan Nanhai Datian Chemical Co., Ltd., model AT-86S; epoxy diluent comes from Guangzhou Bangtai New Materials Co., Ltd., brand 802.

[0027] Example 1: A rock wool board prepared using fly ash from garbage incineration and a processing method thereof, comprising the following steps:

[0028] Step 1:

[0029] S11: Collect fly ash from garbage incineration, sieve it with a sieve with a pore size of 3 mm to remove large particles, remove iron-based impurities by magnetic attraction, pickle it with a dilute hydrochloric acid solution with a mass concentration of 1%, and dry it for later use;

[0030] S12: Grinding and sieving the treated waste incineration fly ash, basalt, limestone, slag, clay, gypsum, glass fiber, and pebbles respectively to control the particle size to 100 μm; mixing them according to a weight ratio of 60:20:8:21:6:4:2:1 to form a mixed material; melting the mixed material to obtain a molten liquid, introducing nitrogen for protection during the melting treatment, the melting treatment temperature is 1500° C., and the melting treatment time is 2 h; using a centrifugal flight method to fiberize the molten liquid to obtain fiber filaments with a length of 5 mm;

[0031] Step 2:

[0032] S21: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is dispersed in tetrahydrofuran, the system temperature is controlled to be 10°C, acrylic acid is added dropwise with stirring, and the stirring reaction is continued for 3 hours after the addition is completed. After the reaction is completed, the monocarboxyphosphaphenanthrene is obtained by rotary evaporation at 40°C and constant temperature drying in a drying oven; wherein the molar ratio of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to acrylic acid is 1:1;

[0033] S22: Mix 2,4,6,8-tetramethylcyclotetrasiloxane and allyl glycidyl ether in a molar ratio of 1:4, heat to 50°C, stir for 5 minutes, add Custer catalyst, stir until the temperature stabilizes, and continue the reaction for 3 hours to obtain tetraepoxy-grafted siloxane;

[0034] S23: dispersing tetraepoxy-grafted siloxane and monocarboxyphosphaphenanthrene in anhydrous toluene, adding a catalyst benzyltriethylammonium chloride, heating to 100° C. and reacting for 3 hours to obtain phosphaphenanthrene-grafted silicone; wherein the tetraepoxy-grafted siloxane and monocarboxyphosphaphenanthrene are reacted at a molar ratio of epoxy group to carboxyl group of 2:1;

[0035] S24: Melting magnolol at 160° C., adding phosphaphenanthrene grafted silicone with stirring, reacting for 24 hours with butyltriphenylphosphonium bromide as a catalyst, washing with deionized water after cooling, and drying to obtain an epoxy-based silicon-containing flame retardant oligomer; wherein magnolol and phosphaphenanthrene grafted silicone are reacted at a molar ratio of phenolic hydroxyl group to epoxy group of 1:2;

[0036] Step 3:

[0037] S31: 100 g of epoxy resin E51, 47 g of curing agent, 1 g of defoaming agent, and 7 g of epoxy diluent are mixed, and then epoxy-based silicon-containing flame retardant oligomer is added to obtain epoxy resin mixed glue; wherein the total weight of the epoxy-based silicon-containing flame retardant oligomer is 8% of the total weight of the epoxy resin E51;

[0038] S32: According to the weight percentage, 15% epoxy resin mixed glue and 85% fiber filaments are mixed and fed and compressed into a mold with a compression pressure of 5 MPa; the mixture is cured at 150°C for 2 hours and cooled to obtain the product.

[0039] Embodiment 2: A rock wool board prepared by using fly ash from garbage incineration and a processing method thereof, comprising the following steps:

[0040] Step 1:

[0041] S11: Collect fly ash from garbage incineration, sieve it with a sieve with a pore size of 3 mm to remove large particles, remove iron-based impurities by magnetic attraction, pickle it with a dilute hydrochloric acid solution with a mass concentration of 1%, and dry it for later use;

[0042] S12: Grinding and sieving the treated waste incineration fly ash, basalt, limestone, slag, clay, gypsum, glass fiber, and pebbles respectively to control the particle size to 100 μm; mixing them according to a weight ratio of 60:20:8:21:6:4:2:1 to form a mixed material; melting the mixed material to obtain a molten liquid, introducing nitrogen for protection during the melting treatment, the melting treatment temperature is 1550° C., and the melting treatment time is 2.5 h; using a centrifugal flight method to fiberize the molten liquid to obtain fiber filaments with a length of 5 mm;

[0043] Step 2:

[0044] S21: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is dispersed in tetrahydrofuran, the system temperature is controlled to be 10°C, acrylic acid is added dropwise with stirring, and the stirring reaction is continued for 3.5 hours after the addition is completed. After the reaction is completed, the monocarboxyphosphaphenanthrene is obtained by rotary evaporation at 45°C and constant temperature drying in a drying oven; wherein the molar ratio of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to acrylic acid is 1:1;

[0045] S22: Mix 2,4,6,8-tetramethylcyclotetrasiloxane and allyl glycidyl ether in a molar ratio of 1:4, heat to 55°C, stir for 8 minutes, add Custer catalyst, stir until the temperature stabilizes, and continue the reaction for 4 hours to obtain tetraepoxy-grafted siloxane;

[0046] S23: dispersing tetraepoxy-grafted siloxane and monocarboxyphosphaphenanthrene in anhydrous toluene, adding a catalyst benzyltriethylammonium chloride, heating to 105° C. for reaction for 4 hours to obtain phosphaphenanthrene-grafted silicone; wherein the tetraepoxy-grafted siloxane and monocarboxyphosphaphenanthrene are reacted at a molar ratio of epoxy group to carboxyl group of 2:1;

[0047] S24: Melting magnolol at 165° C., adding phosphaphenanthrene grafted silicone with stirring, reacting for 30 hours with butyltriphenylphosphonium bromide as a catalyst, washing with deionized water after cooling, and drying to obtain an epoxy-based silicon-containing flame retardant oligomer; wherein magnolol and phosphaphenanthrene grafted silicone are reacted at a molar ratio of phenolic hydroxyl group to epoxy group of 1:2;

[0048] Step 3:

[0049] S31: 100 g of epoxy resin E51, 47 g of curing agent, 1 g of defoaming agent, and 7 g of epoxy diluent are mixed, and then epoxy-based silicon-containing flame retardant oligomer is added to obtain epoxy resin mixed glue; wherein the total weight of the epoxy-based silicon-containing flame retardant oligomer is 10% of the total weight of the epoxy resin E51;

[0050] S32: According to the weight percentage, 15% epoxy resin mixed glue and 85% fiber filaments are mixed and fed and compressed into a mold with a compression pressure of 7 MPa; the mixture is cured at 170°C for 2.5 hours and cooled to obtain the product.

[0051] Embodiment 3: A rock wool board prepared by using fly ash from garbage incineration and a processing method thereof, comprising the following steps:

[0052] Step 1:

[0053] S11: Collect fly ash from garbage incineration, sieve it with a sieve with a pore size of 3 mm to remove large particles, remove iron-based impurities by magnetic attraction, pickle it with a dilute hydrochloric acid solution with a mass concentration of 1%, and dry it for later use;

[0054] S12: Grinding and sieving the treated waste incineration fly ash, basalt, limestone, slag, clay, gypsum, glass fiber, and pebbles respectively to control the particle size to 100 μm; mixing them according to a weight ratio of 60:20:8:21:6:4:2:1 to form a mixed material; melting the mixed material to obtain a molten liquid, introducing nitrogen for protection during the melting treatment, the melting treatment temperature is 1600° C., and the melting treatment time is 3 hours; using a centrifugal flight method to fiberize the molten liquid to obtain fiber filaments with a length of 5 mm;

[0055] Step 2:

[0056] S21: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is dispersed in tetrahydrofuran, the system temperature is controlled to be 10°C, acrylic acid is added dropwise with stirring, and the stirring reaction is continued for 4 hours after the addition is completed. After the reaction is completed, the monocarboxyphosphaphenanthrene is obtained by rotary evaporation at 50°C and constant temperature drying in a drying oven; wherein the molar ratio of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to acrylic acid is 1:1;

[0057] S22: Mix 2,4,6,8-tetramethylcyclotetrasiloxane and allyl glycidyl ether in a molar ratio of 1:4, heat to 60°C, stir for 10 minutes, add Custer catalyst, stir until the temperature stabilizes, and continue the reaction for 5 hours to obtain tetraepoxy-grafted siloxane;

[0058] S23: dispersing tetraepoxy-grafted siloxane and monocarboxyphosphaphenanthrene in anhydrous toluene, adding a catalyst benzyltriethylammonium chloride, heating to 110° C. for reaction for 5 hours to obtain phosphaphenanthrene-grafted silicone; wherein the tetraepoxy-grafted siloxane and monocarboxyphosphaphenanthrene are reacted at a molar ratio of epoxy group to carboxyl group of 2:1;

[0059] S24: Melting magnolol at 170° C., adding phosphaphenanthrene grafted silicone with stirring, reacting for 36 hours with butyltriphenylphosphonium bromide as a catalyst, washing with deionized water after cooling, and drying to obtain an epoxy-containing silicon flame retardant oligomer; wherein magnolol and phosphaphenanthrene grafted silicone are reacted at a molar ratio of phenolic hydroxyl group to epoxy group of 1:2;

[0060] Step 3:

[0061] S31: 100 g of epoxy resin E51, 47 g of curing agent, 1 g of defoaming agent, and 7 g of epoxy diluent are mixed, and then epoxy-based silicon-containing flame retardant oligomer is added to obtain epoxy resin mixed glue; wherein the total weight of the epoxy-based silicon-containing flame retardant oligomer is 12% of the total weight of the epoxy resin E51;

[0062] S32: According to the weight percentage, 15% epoxy resin mixed glue and 85% fiber filaments are mixed and fed and compressed into a mold with a compression pressure of 8 MPa; the mixture is cured at 180°C for 3 hours and cooled to obtain the product.

[0063] Comparative Example 1: No epoxy-based silicon-containing flame retardant oligomer was added, and other parameters were the same as those in Example 1.

[0064] Step 1:

[0065] S11: Collect fly ash from garbage incineration, sieve it with a sieve with a pore size of 3 mm to remove large particles, remove iron-based impurities by magnetic attraction, pickle it with a dilute hydrochloric acid solution with a mass concentration of 1%, and dry it for later use;

[0066] S12: Grinding and sieving the treated waste incineration fly ash, basalt, limestone, slag, clay, gypsum, glass fiber, and pebbles respectively to control the particle size to 100 μm; mixing them according to a weight ratio of 60:20:8:21:6:4:2:1 to form a mixed material; melting the mixed material to obtain a molten liquid, introducing nitrogen for protection during the melting treatment, the melting treatment temperature is 1500° C., and the melting treatment time is 2 h; using a centrifugal flight method to fiberize the molten liquid to obtain fiber filaments with a length of 5 mm;

[0067] Step 2:

[0068] S31: 100 g of epoxy resin E51, 47 g of curing agent, 1 g of defoaming agent, and 7 g of epoxy diluent are mixed to obtain an epoxy resin mixed glue solution;

[0069] S32: According to the weight percentage, 15% epoxy resin mixed glue and 85% fiber filaments are mixed and fed and compressed into a mold with a compression pressure of 5 MPa; the mixture is cured at 150°C for 2 hours and cooled to obtain the product.

[0070] Comparative Example 2: The amount of epoxy-based silicon-containing flame retardant oligomer was increased, and the other parameters were the same as those in Example 2.

[0071] Step 1:

[0072] S11: Collect fly ash from garbage incineration, sieve it with a sieve with a pore size of 3 mm to remove large particles, remove iron-based impurities by magnetic attraction, pickle it with a dilute hydrochloric acid solution with a mass concentration of 1%, and dry it for later use;

[0073] S12: Grinding and sieving the treated waste incineration fly ash, basalt, limestone, slag, clay, gypsum, glass fiber, and pebbles respectively to control the particle size to 100 μm; mixing them according to a weight ratio of 60:20:8:21:6:4:2:1 to form a mixed material; melting the mixed material to obtain a molten liquid, introducing nitrogen for protection during the melting treatment, the melting treatment temperature is 1550° C., and the melting treatment time is 2.5 h; using a centrifugal flight method to fiberize the molten liquid to obtain fiber filaments with a length of 5 mm;

[0074] Step 2:

[0075] S21: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is dispersed in tetrahydrofuran, the system temperature is controlled to be 10°C, acrylic acid is added dropwise with stirring, and the stirring reaction is continued for 3.5 hours after the addition is completed. After the reaction is completed, the monocarboxyphosphaphenanthrene is obtained by rotary evaporation at 45°C and constant temperature drying in a drying oven; wherein the molar ratio of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to acrylic acid is 1:1;

[0076] S22: Mix 2,4,6,8-tetramethylcyclotetrasiloxane and allyl glycidyl ether in a molar ratio of 1:4, heat to 55°C, stir for 8 minutes, add Custer catalyst, stir until the temperature stabilizes, and continue the reaction for 4 hours to obtain tetraepoxy-grafted siloxane;

[0077] S23: dispersing tetraepoxy-grafted siloxane and monocarboxyphosphaphenanthrene in anhydrous toluene, adding a catalyst benzyltriethylammonium chloride, heating to 105° C. for reaction for 4 hours to obtain phosphaphenanthrene-grafted silicone; wherein the tetraepoxy-grafted siloxane and monocarboxyphosphaphenanthrene are reacted at a molar ratio of epoxy group to carboxyl group of 2:1;

[0078] S24: Melting magnolol at 165° C., adding phosphaphenanthrene grafted silicone with stirring, reacting for 30 hours with butyltriphenylphosphonium bromide as a catalyst, washing with deionized water after cooling, and drying to obtain an epoxy-based silicon-containing flame retardant oligomer; wherein magnolol and phosphaphenanthrene grafted silicone are reacted at a molar ratio of phenolic hydroxyl group to epoxy group of 1:2;

[0079] Step 3:

[0080] S31: 100 g of epoxy resin E51, 47 g of curing agent, 1 g of defoaming agent, and 7 g of epoxy diluent are mixed, and then epoxy-based silicon-containing flame retardant oligomer is added to obtain epoxy resin mixed glue; wherein the total weight of the epoxy-based silicon-containing flame retardant oligomer is 20% of the total weight of the epoxy resin E51;

[0081] S32: According to the weight percentage, 15% epoxy resin mixed glue and 85% fiber filaments are mixed and fed and compressed into a mold with a compression pressure of 7 MPa; the mixture is cured at 170°C for 2.5 hours and cooled to obtain the product.

[0082] Comparative Example 3: Phosphaphenanthrene grafted silicone was used instead of epoxy-based silicon-containing flame retardant oligomer, and the other parameters were the same as those in Example 3.

[0083] Step 1:

[0084] S11: Collect fly ash from garbage incineration, sieve it with a sieve with a pore size of 3 mm to remove large particles, remove iron-based impurities by magnetic attraction, pickle it with a dilute hydrochloric acid solution with a mass concentration of 1%, and dry it for later use;

[0085] S12: Grinding and sieving the treated waste incineration fly ash, basalt, limestone, slag, clay, gypsum, glass fiber, and pebbles respectively to control the particle size to 100 μm; mixing them according to a weight ratio of 60:20:8:21:6:4:2:1 to form a mixed material; melting the mixed material to obtain a molten liquid, introducing nitrogen for protection during the melting treatment, the melting treatment temperature is 1600° C., and the melting treatment time is 3 hours; using a centrifugal flight method to fiberize the molten liquid to obtain fiber filaments with a length of 5 mm;

[0086] Step 2:

[0087] S21: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is dispersed in tetrahydrofuran, the system temperature is controlled to be 10°C, acrylic acid is added dropwise with stirring, and the stirring reaction is continued for 4 hours after the addition is completed. After the reaction is completed, the monocarboxyphosphaphenanthrene is obtained by rotary evaporation at 50°C and constant temperature drying in a drying oven; wherein the molar ratio of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to acrylic acid is 1:1;

[0088] S22: Mix 2,4,6,8-tetramethylcyclotetrasiloxane and allyl glycidyl ether in a molar ratio of 1:4, heat to 60°C, stir for 10 minutes, add Custer catalyst, stir until the temperature stabilizes, and continue the reaction for 5 hours to obtain tetraepoxy-grafted siloxane;

[0089] S23: dispersing tetraepoxy-grafted siloxane and monocarboxyphosphaphenanthrene in anhydrous toluene, adding a catalyst benzyltriethylammonium chloride, heating to 110° C. for reaction for 5 hours to obtain phosphaphenanthrene-grafted silicone; wherein the tetraepoxy-grafted siloxane and monocarboxyphosphaphenanthrene are reacted at a molar ratio of epoxy group to carboxyl group of 2:1;

[0090] Step 3:

[0091] S31: 100 g of epoxy resin E51, 47 g of curing agent, 1 g of defoaming agent, and 7 g of epoxy diluent are mixed, and then phosphaphenanthrene grafted silicone is added to obtain epoxy resin mixed glue; wherein the total weight of epoxy-based silicon-containing flame retardant oligomer is 12% of the total weight of epoxy resin E51;

[0092] S32: According to the weight percentage, 15% epoxy resin mixed glue and 85% fiber filaments are mixed and fed and compressed into a mold with a compression pressure of 8 MPa; the mixture is cured at 180°C for 3 hours and cooled to obtain the product.

[0093] Experiment: Samples with a size of 10 cm×10 cm×0.5 cm prepared in Examples 1 to 3 and Comparative Examples 1 to 3 were tested for performance.

[0094] Flame retardant performance: When the ambient temperature is set at 25℃±1℃ and the air humidity is 50±1%, the sample is ignited with a fire source. After the sample burns for 3s, the fire source is removed and the flame extinguishing time is started. The combustion of the test piece is observed throughout the process. Three parallel experiments are performed for each type and the average value is taken.

[0095] Compression strength: The rock wool board is subjected to compression performance test. The test method refers to the standard GB / T 13480-2014 "Determination of compression performance of thermal insulation products for building use".

[0096] Heat resistance: measured by thermogravimetric analyzer, take 20 mg sample, set the protective gas to N2, the gas flow rate to 10 mL / min, the temperature rise range to 25~800℃, the heating rate to 5℃ / min, and record the temperature Td at which the heat loss is 5% 5% .

[0097] The experimental results are shown in Table 1 below.

[0098] Table 1. Test results of various properties of rock wool board

[0099]

[0100] Conclusion: The data of Examples 1 to 3 show that the rock wool board prepared by the present invention has good performance and meets the application requirements. The data of Example 1 and Comparative Example 1 show that after adding the epoxy-based silicon-containing flame retardant oligomer, the various properties of the rock wool board are improved; the data of Example 2 and Comparative Example 2 show that the compression strength of the rock wool board decreases when the amount of epoxy-based silicon-containing flame retardant oligomer is increased; the data of Example 3 and Comparative Example 3 show that the epoxy-based silicon-containing flame retardant oligomer contains magnolol, which improves the strength and heat resistance of the epoxy resin, so the compression strength and heat resistance of the rock wool board are better.

[0101] Finally, it should be noted that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art can still modify the technical solutions described in the aforementioned embodiments or replace some of the technical features therein by equivalents. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for preparing rock wool board using fly ash from garbage incineration, characterized in that: The following steps are involved: Step 1: S11: Collect fly ash from garbage incineration, sieve it with a sieve with an aperture of 3-5 mm to remove large particles, remove iron-based impurities by magnetic attraction, pickle it with a dilute hydrochloric acid solution with a mass concentration of 1-3%, and dry it for later use; S12: grinding and sieving the treated waste incineration fly ash, basalt, limestone, slag, clay, gypsum, glass fiber and pebbles respectively to form a mixed material; melting the mixed material to obtain a molten liquid, introducing nitrogen for protection during the melting treatment, the melting treatment temperature is 1500-1600° C., and the melting treatment time is 2-3 hours; using a centrifugal flight method to fiberize the molten liquid to obtain fiber filaments; Step 2: S21: mixing epoxy resin E51, curing agent, defoaming agent and epoxy diluent, and adding epoxy-based silicon-containing flame retardant oligomer to obtain epoxy resin mixed glue; The method for preparing the epoxy-based silicon-containing flame retardant oligomer comprises the following steps: Step a. Disperse 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in tetrahydrofuran, control the system temperature to 8-12°C, drip acrylic acid with stirring, and continue stirring to react for 3-4 hours after the addition is complete. After the reaction is completed, rotary evaporate at 40-50°C and dry in a drying oven at a constant temperature to obtain monocarboxyphosphaphenanthrene; Step b. Mix 2,4,6,8-tetramethylcyclotetrasiloxane and allyl glycidyl ether, heat to 50-60°C, stir for 5-10 minutes, add Custer catalyst, stir until the temperature stabilizes, and continue the reaction for 3-5 hours to obtain tetraepoxy-grafted siloxane; Step c. dispersing tetraepoxy-grafted siloxane and monocarboxylphosphaphenanthrene in anhydrous toluene, adding a catalyst benzyltriethylammonium chloride, heating to 100-110° C. for reaction for 3-5 hours to obtain phosphaphenanthrene-grafted silicone; wherein the tetraepoxy-grafted siloxane and monocarboxylphosphaphenanthrene react at a molar ratio of epoxy group to carboxyl group of 2:1; Step d. Melting magnolol at 160-170° C., adding phosphaphenanthrene grafted silicone with stirring, reacting for 24-36 hours with butyltriphenylphosphonium bromide as a catalyst, washing with deionized water after cooling, and drying to obtain an epoxy-containing silicon flame retardant oligomer; S22: According to the weight percentage, 10-15% epoxy resin mixed glue and 85-90% fiber filaments are mixed and fed and compressed into a mold with a compression pressure of 5-8 MPa; the mixture is cured at 150-180°C for 2-3 hours and cooled to obtain the product.

2. A method for preparing rock wool board using fly ash from garbage incineration according to claim 1, characterized in that: In S12, the treated waste incineration fly ash, basalt, limestone, slag, clay, gypsum, glass fiber, and pebbles are ground and sieved respectively to control the particle size to 80-120 μm, and are mixed according to the weight ratio of (57-60): (20-30): (5-10): (15-25): (5-8): (3-5): (1-3): (1-2); the melt is fiberized to obtain a fiber length of 5-20 mm.

3. The method for preparing rock wool board using fly ash from garbage incineration according to claim 1, characterized in that: In S21, the contents of the components in the epoxy resin mixed glue are, by weight, 100 parts of epoxy resin E51, 45-52 parts of curing agent, 0.5-1 part of defoaming agent, and 5-8 parts of epoxy diluent; the total weight of the epoxy-based silicon-containing flame retardant oligomer is 8-12% of the total weight of the epoxy resin E51.

4. The method for preparing rock wool board using fly ash from garbage incineration according to claim 1, characterized in that: In step a, the molar ratio of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to acrylic acid is 1:

1.

5. The method for preparing rock wool board using fly ash from garbage incineration according to claim 1, characterized in that: In step b, 2,4,6,8-tetramethylcyclotetrasiloxane and allyl glycidyl ether are mixed in a molar ratio of 1:

4.

6. The method for preparing rock wool board using fly ash from garbage incineration according to claim 1, characterized in that: In step d, magnolol and phosphaphenanthrene grafted silicone are reacted in a molar ratio of phenolic hydroxyl group to epoxy group of 1:

2.

7. The rock wool board obtained by the processing method according to any one of claims 1 to 6.

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