A fire-retardant thermal insulation polyurethane edge-banded sandwich panel, and a preparation method and application thereof

Abstract

The application relates to the technical field of layered composite material preparation, and discloses a flame-retardant thermal-insulation polyurethane edge-sealing sandwich panel and a preparation method and application thereof. The preparation method comprises the following steps: mixing polyether polyol, a flame-retardant filler, modified epoxy resin, a catalyst, a foaming agent and a bubble uniformizing agent to obtain A material, adding B material into the A material to obtain polyurethane-based glue; combining an upper panel, a sandwich layer and a lower panel, adopting the polyurethane-based glue to perform edge sealing and curing to obtain the flame-retardant thermal-insulation polyurethane edge-sealing sandwich panel. The edge-sealing sandwich panel has excellent flame-retardant and thermal-insulation performances, and has excellent comprehensive performance in fire prevention, thermal insulation, installation efficiency and service life, and is especially suitable for industrial upgrading and green building fields. The polyurethane-based glue can obtain hard-foam flame-retardant thermal-insulation polyurethane material after curing, and the mechanical performance and the flame-retardant and thermal-insulation performances are good.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of layered composite material preparation, in particular to a flame-retardant thermal-insulation polyurethane edge-sealed sandwich panel and a preparation method and application thereof. BACKGROUND

[0002] The integrated panel is a multi-layer composite thermal-insulation panel produced by a factory assembly line, mainly composed of a thermal-insulation core material (such as rock wool, EPS) having a thermal-insulation function and a decorative layer (such as fluorocarbon decoration, metal decoration) serving as decoration, and has high consistency, short construction period, low construction cost, high installation efficiency, and excellent thermal-insulation performance.

[0003] The polyurethane edge-sealed sandwich panel is one of the integrated panels, and the prior art such as Chinese Patent Application CN102873973A discloses a sandwich panel edge-sealing method, which sprays liquid polyurethane liquid to both sides of the sandwich panel to make the polyurethane liquid foam and form, and fills both sides of the sandwich panel, so that the sandwich panel prepared has improved air tightness, water tightness, and bonding force at the panel lapping (insertion) position, effectively prevents the occurrence of cold bridge phenomenon, and overcomes the separation of the steel plate and the core material during installation and transportation. However, the polyurethane liquid used in the prior art lacks flame-retardant components, and the flame-retardant performance of the sandwich panel prepared needs to be improved. SUMMARY

[0004] The present application aims to overcome the deficiencies of the prior art, and provides a flame-retardant thermal-insulation polyurethane edge-sealed sandwich panel and a preparation method and application thereof. The flame-retardant thermal-insulation polyurethane edge-sealed sandwich panel has a three-layer structure, including an upper panel, a sandwich layer, and a lower panel, and is prepared by edge sealing and curing with polyurethane-based glue, has excellent flame-retardant and thermal-insulation performance, and has excellent comprehensive performance in fire prevention, thermal insulation, installation efficiency, and service life, and is particularly suitable for industrial upgrading and green building fields. The polyurethane-based glue can obtain a rigid foam flame-retardant thermal-insulation polyurethane material after curing, and has good mechanical performance and flame-retardant and thermal-insulation performance.

[0005] To achieve the above-mentioned purposes, the technical solutions adopted by the present application are as follows:

[0006] A preparation method of a flame-retardant thermal-insulation polyurethane material, comprising the following steps:

[0007] Step (1), mixing expanded perlite, γ-aminopropyltriethoxysilane, ethanol, and water, ultrasonic dispersion, reaction, filtering, washing, and drying to obtain amino expanded perlite;

[0008] Mixing the amino expanded perlite and N,N-dimethylformamide, ultrasonic dispersion, adding dimethyl chlorophosphate and triethylamine, reaction, filtering, washing, and drying to obtain phosphate ester modified expanded perlite;

[0009] Step (2), mixing and dissolving melamine, paraformaldehyde and water, adding a regulator to adjust pH value, reacting, after the reaction is completed, adding dropwise diethanolamine aqueous solution, after the dropwise addition is completed, continuing to react, after the reaction is completed, rotary evaporation, to obtain the flame retardant;

[0010] Mixing and reacting phosphate ester modified expanded perlite, flame retardant, sodium hydroxide and N,N-dimethylformamide, after the reaction is completed, filtering, washing, drying, to obtain the flame retardant / expanded perlite composite material; mixing the flame retardant / expanded perlite composite material with graphene, to obtain the flame retardant filler;

[0011] Step (3), mixing and stirring polyether polyol, flame retardant filler, modified epoxy resin, catalyst, foaming agent and bubble uniformizer, to obtain A material;

[0012] Adding B material into A material, stirring and mixing uniformly, to obtain polyurethane-based glue; placing the polyurethane-based glue in a mold, curing, to obtain the flame-retardant thermal insulation polyurethane material.

[0013] Preferably, in the step (1), when preparing the amino expanded perlite, the mass ratio of expanded perlite, γ-aminopropyltriethoxysilane, ethanol and water is 1:0.8-1:15-20:1; the reaction condition is stirring and reacting at 70-80℃ for 3-4h.

[0014] Preferably, in the step (1), when preparing the phosphate ester modified expanded perlite, the mass ratio of amino expanded perlite, N,N-dimethylformamide, dimethyl chlorophosphate and triethylamine is 10:190-220:7.5-8:8.8-9.2; the reaction condition is reacting at 20-30℃ for 24-30h.

[0015] Preferably, in the step (2), when preparing the flame retardant, the mass ratio of melamine, paraformaldehyde, water and diethanolamine aqueous solution is 12.6:9-9.5:180-200:30.7-31; the diethanolamine aqueous solution is 35wt% diethanolamine aqueous solution, the dropwise addition time is 10-20min; the reaction condition is stirring and reacting at pH value of 8.5-9 and temperature of 60-65℃ for 2-2.5h, the continued reaction condition is continuing to react at temperature of 60-65℃ for 3h.

[0016] Preferably, the regulator comprises triethylamine.

[0017] Preferably, in the step (2), when preparing the flame retardant / expanded perlite composite material, the mass ratio of phosphate ester modified expanded perlite, flame retardant, sodium hydroxide and N,N-dimethylformamide is 8-10:28-30:1.2-1.3:100-120; the reaction condition is reacting at set temperature of 150-160℃ for 18h.

[0018] Preferably, in the step (2), the mass ratio of the flame retardant / expanding perlite composite to graphene is 10:1-1.5.

[0019] Preferably, in the step (3), the foaming agent is water; the catalyst is 2-ethyl-4-methyl imidazole, 2,4,6-tris(dimethylaminomethyl)phenol, and triethylenediamine compounded in a mass ratio of 2-2.5:0.45:0.7-1; and in the preparation of the A material, the stirring condition is that stirring is carried out at a rotating speed of 4000-5000 r / min for 20-30 min.

[0020] Preferably, in the step (3), the modified epoxy resin is prepared by the following steps:

[0021] The trimethylolpropane triglycidyl ether and binaphthol are mixed uniformly, tetrabutylammonium bromide is added, and then the reaction is carried out. After the reaction is completed, ethyl triphenylphosphonium bromide is added, and then the reaction is continued. After the reaction is completed, the reaction system is cooled to room temperature to obtain the hyperbranched epoxy resin. The hyperbranched epoxy resin is mixed with the epoxy resin E51 to obtain the modified epoxy resin.

[0022] Preferably, in the step (3), in the preparation of the modified epoxy resin, the molar ratio of the trimethylolpropane triglycidyl ether to the binaphthol is 2.7-2.8:1; the uniform mixing condition is that the mixing is carried out under a nitrogen atmosphere at a temperature of 100℃; the reaction condition is that the reaction is carried out under a nitrogen atmosphere at a temperature of 110-120℃ for 2-3 h; the continuous reaction condition is that the temperature is increased to 140-150℃ at a rate of 1℃ / min, and then the reaction is continued for 2-2.5 h; and the mass ratio of the hyperbranched epoxy resin to the epoxy resin E51 is 7-9:91-93.

[0023] Preferably, in the step (3), in the preparation of the modified epoxy resin, the mass sum of the tetrabutylammonium bromide and the ethyl triphenylphosphonium bromide is 0.06-0.08% of the mass sum of the trimethylolpropane triglycidyl ether and the binaphthol; and the mass ratio of the tetrabutylammonium bromide to the ethyl triphenylphosphonium bromide is 1.6:1.

[0024] Preferably, in the step (3), the B material is a polymethylene polyphenyl polyisocyanate; and the mass ratio of the polyether polyol, the flame-retardant filler, the modified epoxy resin, the catalyst, the foaming agent, the foam stabilizer, and the polymethylene polyphenyl polyisocyanate is 100:4-6:8-10:3-4:3.5-4:0.5-1:110-120; and in the preparation of the polyurethane-based glue, the stirring condition is that stirring is carried out at a rotating speed of 4000-5000 r / min for 20 s; and the curing condition is that curing is carried out at a temperature of 120℃ for 1-2 h, and then curing is continued for 3-4 h after the mold is opened.

[0025] Preferably, the fire-retardant thermal insulation polyurethane material is prepared by the preparation method of the fire-retardant thermal insulation polyurethane material.

[0026] Preferably, the fire-retardant thermal insulation polyurethane material is prepared by the preparation method of the fire-retardant thermal insulation polyurethane material.

[0027] The application discloses a preparation method of a fire-retardant thermal insulation polyurethane edge-sealed sandwich board by using the polyurethane-based glue.

[0028] The upper panel, the sandwich layer and the lower panel are combined in the order of the upper panel, the sandwich layer and the lower panel, edge sealing is performed on the combined material by using the polyurethane-based glue, and curing is performed to obtain the fire-retardant thermal insulation polyurethane edge-sealed sandwich board.

[0029] Preferably, the curing condition is that curing is performed at 120 DEG C for 4-5 h.

[0030] Preferably, the fire-retardant thermal insulation polyurethane edge-sealed sandwich board is prepared by the preparation method of the fire-retardant thermal insulation polyurethane edge-sealed sandwich board.

[0031] Preferably, the fire-retardant thermal insulation polyurethane edge-sealed sandwich board is prepared by the preparation method of the fire-retardant thermal insulation polyurethane edge-sealed sandwich board.

[0032] Compared with the prior art, the application has the beneficial effects that:

[0033] 1、The fire-retardant thermal insulation polyurethane material is prepared by the preparation method of the fire-retardant thermal insulation polyurethane material.

[0034] 2、The application is in preparation of the flame-retardant filler, the expanded perlite is surface modified by using gamma-aminopropyl triethoxysilane, the amino functional group is introduced on the surface, the amino expanded perlite is obtained, and the nucleophilic substitution reaction further occurs between the amino expanded perlite and dimethyl chlorophosphate, the methyl phosphate group is introduced on the surface of the expanded perlite, the phosphate ester modified expanded perlite is obtained, the flame retardant containing the polyhydroxy structure is prepared by the reaction of melamine, polyformaldehyde and diethanolamine, the ester exchange reaction occurs between the flame retardant and the phosphate ester modified expanded perlite, the flame-retardant functional group is grafted on the surface of the expanded perlite, the flame-retardant filler obtained after compounding with the graphene has better compatibility and dispersibility with the matrix material, the inorganic flame-retardant material expanded perlite and the organic flame retardant are linked through the covalent bond, not only have the synergistic flame-retardant effect, but also reduce the migration of the organic flame retardant and improve the long-acting performance of the flame-retardant material.

[0035] 3、The application is in preparation of the flame-retardant filler, the expanded perlite is surface modified by using gamma-aminopropyl triethoxysilane, the amino functional group is introduced on the surface, the amino expanded perlite is obtained, and the nucleophilic substitution reaction further occurs between the amino expanded perlite and dimethyl chlorophosphate, the methyl phosphate group is introduced on the surface of the expanded perlite, the phosphate ester modified expanded perlite is obtained, the flame retardant containing the polyhydroxy structure is prepared by the reaction of melamine, polyformaldehyde and diethanolamine, the ester exchange reaction occurs between the flame retardant and the phosphate ester modified expanded perlite, the flame-retardant functional group is grafted on the surface of the expanded perlite, the flame-retardant filler obtained after compounding with the graphene has better compatibility and dispersibility with the matrix material, the inorganic flame-retardant material expanded perlite and the organic flame retardant are linked through the covalent bond, not only have the synergistic flame-retardant effect, but also reduce the migration of the organic flame retardant and improve the long-acting performance of the flame-retardant material. BRIEF DESCRIPTION OF DRAWINGS

[0036] Figure 1 is the structural schematic diagram of the flame-retardant and thermal-insulating polyurethane edge sealing sandwich board prepared in the application;

[0037] Figure 2 is the compression strength fold line graph of example 1-4 and comparative example 1-2 in the performance test in the application;

[0038] Figure 3 is the thermal conductivity column chart of example 1-4 and comparative example 1-2 in the performance test in the application;

[0039] Figure 4 is the limiting oxygen index column chart of example 1-4 and comparative example 1-2 in the performance test in the application;

[0040] in the figure:

[0041] 1, upper panel; 2, flame-retardant and thermal-insulating polyurethane material formed after curing of polyurethane-based glue; 3, sandwich layer; 4, lower panel. DETAILED DESCRIPTION

[0042] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments of the present application, all other embodiments obtained by a person of ordinary skill in the art without creative work fall within the protection scope of the present application.

[0043] Embodiment 1

[0044] The present embodiment discloses a preparation method of a flame-retardant thermal-insulation polyurethane material, comprising the following steps:

[0045] Step (1), expand perlite, gamma-aminopropyltriethoxysilane, ethanol and water are mixed in a mass ratio of 1:0.8:15:1, ultrasonic dispersion is performed for 10 min, stirring reaction is performed at a temperature of 70 DEG C for 4 h, after the reaction is completed, filtration is performed, the filter cake is taken, 10 times the mass of the filter cake of water is added for washing, drying is performed at a temperature of 50 DEG C for 24 h, and amino expand perlite is obtained;

[0046] The amino expand perlite and N,N-dimethylformamide are mixed, ultrasonic dispersion is performed for 10 min, dimethyl chlorophosphate and triethylamine are added, reaction is performed at a temperature of 20 DEG C for 30 h, after the reaction is completed, filtration is performed, the filter cake is taken, 10 times the mass of the filter cake of ethanol is added for washing, drying is performed at a temperature of 50 DEG C for 24 h, and phosphate ester modified expand perlite is obtained;

[0047] The mass ratio of the amino expand perlite, N,N-dimethylformamide, dimethyl chlorophosphate and triethylamine is 10:190:7.5:8.8;

[0048] Step (2), melamine, polyformaldehyde and water are mixed and dissolved, triethylamine is added to adjust the pH value to 8.5, stirring reaction is performed at a temperature of 60 DEG C for 2.5 h, after the reaction is completed, 35wt% diethanolamine aqueous solution is added dropwise, the dropwise adding time is 10 min, after the dropwise adding is completed, reaction is continuously performed at a temperature of 60 DEG C for 3 h, after the reaction is completed, triethylamine and water are removed by rotary evaporation, and a flame retardant is obtained;

[0049] The mass ratio of the melamine, polyformaldehyde, water and 35wt% diethanolamine aqueous solution is 12.6:9:180:30.7;

[0050] The phosphate ester modified expand perlite, the flame retardant, sodium hydroxide and N,N-dimethylformamide are mixed in a mass ratio of 8:28:1.2:100, reaction is performed at a set temperature of 150 DEG C for 18 h, after the reaction is completed, filtration is performed, the filter cake is taken, 10 times the mass of the filter cake of ethanol is added for washing, drying is performed at a temperature of 50 DEG C for 12 h, and a flame retardant / expand perlite composite material is obtained; the flame retardant / expand perlite composite material and graphene are mixed in a mass ratio of 10:1, and a flame-retardant filler is obtained;

[0051] Step (3), mixing the polyether polyol, the flame-retardant filler, the modified epoxy resin, the catalyst, the foaming agent and the cell stabilizer, stirring at a rotating speed of 4000 r / min for 30 min to obtain A material;

[0052] The foaming agent is water; the catalyst is a compound of 2-ethyl-4-methylimidazole, 2,4,6-tris(dimethylaminomethyl)phenol and triethylenediamine with a mass ratio of 2:0.45:1.

[0053] The modified epoxy resin is prepared by the following steps:

[0054] The trimethylolpropane triglycidyl ether and the binaphthyl are mixed uniformly in a nitrogen atmosphere at a temperature of 100℃, and tetrabutylammonium bromide is added. The temperature is increased to 110℃, and the reaction is carried out for 3h. After the reaction is completed, ethyl triphenylphosphonium bromide is added, and the temperature is increased to 140℃ at a rate of 1℃ / min. The reaction is continued for 2.5h, and then the reaction is cooled to room temperature to obtain the hyperbranched epoxy resin. The hyperbranched epoxy resin is mixed with the epoxy resin E51 at a mass ratio of 7:93 to obtain the modified epoxy resin. The mass sum of the tetrabutylammonium bromide and the ethyl triphenylphosphonium bromide is 0.06% of the mass sum of the trimethylolpropane triglycidyl ether and the binaphthyl. The mass ratio of the tetrabutylammonium bromide to the ethyl triphenylphosphonium bromide is 1.6:1.

[0055] The polyurethane-based adhesive is obtained by adding the polymethylene polyphenyl polyisocyanate to the A material and stirring at a rotating speed of 4000 r / min for 20s. The polyurethane-based adhesive is placed in a mold and cured at a temperature of 120℃ for 1h. After the mold is opened, the curing is continued for 4h to obtain the flame-retardant thermal insulation polyurethane material.

[0056] The mass ratio of the polyether polyol, the flame-retardant filler, the modified epoxy resin, the catalyst, the foaming agent, the cell stabilizer and the polymethylene polyphenyl polyisocyanate is 100:4:8:3:3.5:0.5:110.

[0057] Example 2

[0058] The present embodiment discloses a preparation method of a flame-retardant thermal insulation polyurethane material, which comprises the following steps:

[0059] Step (1), mixing the expanded perlite, the γ-aminopropyltriethoxysilane, the ethanol and the water at a mass ratio of 1:0.9:20:1, ultrasonic dispersion for 15 min, stirring reaction at a temperature of 70℃ for 4h. After the reaction is completed, the filter cake is obtained by filtration, and the filter cake is washed with water with a mass of 10 times that of the filter cake. The mixture is dried at a temperature of 50℃ for 24h to obtain the amino expanded perlite.

[0060] The amino expanded perlite, N,N-dimethylformamide are mixed, ultrasonic dispersion is carried out for 15 min, dimethyl chlorophosphate, triethylamine are added, and reaction is carried out for 26 h at a temperature of 25 DEG C; after the reaction is completed, filtration is carried out, the filter cake is taken out, 10 times the mass of ethanol is added to wash, and drying is carried out at a temperature of 55 DEG C for 24 h, to obtain phosphate ester modified expanded perlite;

[0061] The mass ratio of the amino expanded perlite, N,N-dimethylformamide, dimethyl chlorophosphate and triethylamine is 10:200:7.7:9.

[0062] Step (2), melamine, polyformaldehyde and water are mixed and dissolved, triethylamine is added to adjust the pH value to 8.8, and stirring reaction is carried out at a temperature of 60 DEG C for 2.5 h; after the reaction is completed, 35 wt% diethanolamine aqueous solution is added dropwise, the dropwise adding time is 10 min, after the dropwise adding is completed, the reaction is continuously carried out at a temperature of 60 DEG C for 3 h; after the reaction is completed, triethylamine and water are removed by rotary evaporation, to obtain a flame retardant;

[0063] The mass ratio of the melamine, polyformaldehyde, water and 35 wt% diethanolamine aqueous solution is 12.6:9.2:190:30.8.

[0064] The phosphate ester modified expanded perlite, the flame retardant, sodium hydroxide and N,N-dimethylformamide are mixed in a mass ratio of 8:29:1.25:110, and reaction is carried out at a set temperature of 155 DEG C for 18 h; after the reaction is completed, filtration is carried out, the filter cake is taken out, 10 times the mass of ethanol is added to wash, and drying is carried out at a temperature of 55 DEG C for 12 h, to obtain a flame retardant / expanded perlite composite material; the flame retardant / expanded perlite composite material is mixed with graphene in a mass ratio of 10:1, to obtain a flame retardant filler;

[0065] Step (3), the polyether polyol, the flame retardant filler, the modified epoxy resin, the catalyst, the foaming agent and the foam stabilizer are mixed, and stirring is carried out at a rotating speed of 4000 r / min for 30 min, to obtain A material;

[0066] The mass ratio of the foaming agent, the catalyst and triethylene diamine is 2.2:0.45:0.8.

[0067] The modified epoxy resin is prepared by the following steps:

[0068] trimethylolpropane triglycidyl ether, binaphthyl in a molar ratio of 2.7:1 are mixed uniformly in a nitrogen atmosphere at a temperature of 100 DEG C, tetrabutylammonium bromide is added, the temperature is raised to 115 DEG C and reacted for 2.5 h, after the reaction is completed, ethyl triphenylphosphonium bromide is added, the temperature is raised to 140 DEG C at a rate of 1 DEG C / min and reacted for 2.5 h, after the reaction is completed, the temperature is cooled to room temperature, and a hyperbranched epoxy resin is obtained; the hyperbranched epoxy resin is mixed with epoxy resin E51 in a mass ratio of 7.5:92.5 to obtain a modified epoxy resin; wherein the mass sum of tetrabutylammonium bromide and ethyl triphenylphosphonium bromide is 0.06% of the mass sum of trimethylolpropane triglycidyl ether and binaphthyl; the mass ratio of tetrabutylammonium bromide to ethyl triphenylphosphonium bromide is 1.6:1;

[0069] The B material polymethylene polyphenyl polyisocyanate is added to the A material, stirred at a speed of 4000 r / min for 20 s to mix uniformly, and a polyurethane-based glue is obtained; the polyurethane-based glue is placed in a mold, cured at a temperature of 120 DEG C for 1 h, and after the mold is opened, cured for 4 h to obtain a flame-retardant thermal-insulation polyurethane material;

[0070] The mass ratio of the polyether polyol, the flame-retardant filler, the modified epoxy resin, the catalyst, the foaming agent, the foam stabilizer, and the polymethylene polyphenyl polyisocyanate is 100:4.5:8.5:3.3:3.6:0.6:112.

[0071] Example 3

[0072] The present embodiment discloses a preparation method of a flame-retardant thermal-insulation polyurethane material, comprising the following steps:

[0073] Step (1), expandable perlite, gamma-aminopropyl triethoxysilane, ethanol, and water are mixed in a mass ratio of 1:0.9:20:1, ultrasonic dispersion is performed for 15 min, stirring reaction is performed at a temperature of 75 DEG C for 3.5 h, after the reaction is completed, filtration is performed, the filter cake is taken, water with a mass of 10 times that of the filter cake is added for washing, and drying is performed at a temperature of 55 DEG C for 24 h to obtain amino expandable perlite;

[0074] The amino expandable perlite and N,N-dimethylformamide are mixed, ultrasonic dispersion is performed for 15 min, dimethyl chlorophosphate and triethylamine are added, and reaction is performed at a temperature of 25 DEG C for 26 h, after the reaction is completed, filtration is performed, the filter cake is taken, ethanol with a mass of 10 times that of the filter cake is added for washing, and drying is performed at a temperature of 55 DEG C for 24 h to obtain phosphate ester modified expandable perlite;

[0075] The mass ratio of the amino expandable perlite, N,N-dimethylformamide, dimethyl chlorophosphate, and triethylamine is 10:200:7.8:9;

[0076] Step (2), the melamine, paraformaldehyde, water are mixed and dissolved, triethylamine is added to adjust the pH value to 8.8, and stirring is carried out at 60°C for 2.5h. After the reaction is completed, 35wt% diethanolamine aqueous solution is added dropwise for 10min. After the dropwise addition is completed, the reaction is continued at 60°C for 3h. After the reaction is completed, triethylamine and water are removed by rotary evaporation to obtain the flame retardant;

[0077] The mass ratio of the melamine, the paraformaldehyde, the water and the 35wt% diethanolamine aqueous solution is 12.6:9.3:190:30.9.

[0078] The phosphate-modified expanded perlite, the flame retardant, sodium hydroxide and N,N-dimethylformamide are mixed at a mass ratio of 9:29:1.25:110, and reacted at a set temperature of 155°C for 18h. After the reaction is completed, filtration is carried out, the filter cake is taken out, and the filter cake is washed with 10 times the amount of ethanol and dried at 55°C for 12h to obtain the flame retardant / expanded perlite composite material. The flame retardant / expanded perlite composite material is mixed with graphene at a mass ratio of 10:1 to obtain the flame retardant filler.

[0079] Step (3), the polyether polyol, the flame retardant filler, the modified epoxy resin, the catalyst, the foaming agent and the foam stabilizer are mixed and stirred at a rotation speed of 4000r / min for 30min to obtain the A material.

[0080] The foaming agent is water; and the catalyst is a compound of 2-ethyl-4-methylimidazole, 2,4,6-tris(dimethylaminomethyl)phenol and triethylenediamine at a mass ratio of 2.3:0.45:0.9.

[0081] The modified epoxy resin is prepared by the following steps:

[0082] The trimethylolpropane triglycidyl ether and the binaphthol are mixed uniformly at a molar ratio of 2.75:1 in a nitrogen atmosphere at 100°C, and tetrabutylammonium bromide is added. The temperature is increased to 115°C and reacted for 2.5h. After the reaction is completed, ethyl triphenylphosphonium bromide is added, and the temperature is increased to 145°C at a rate of 1°C / min and reacted for 2.3h. After the reaction is completed, the temperature is cooled to room temperature to obtain the hyperbranched epoxy resin. The hyperbranched epoxy resin is mixed with the epoxy resin E51 at a mass ratio of 8:92 to obtain the modified epoxy resin. The mass sum of the tetrabutylammonium bromide and the ethyl triphenylphosphonium bromide is 0.06% of the mass sum of the trimethylolpropane triglycidyl ether and the binaphthol. The mass ratio of the tetrabutylammonium bromide to the ethyl triphenylphosphonium bromide is 1.6:1.

[0083] The B material polymethylene polyphenyl polyisocyanate is added into the A material, and is stirred at a rotating speed of 4000 r / min for 20 s to be uniformly mixed to obtain a polyurethane-based glue; the polyurethane-based glue is placed in a mold, and is cured at a temperature of 120℃ for 1 h, and after the mold is opened, curing is continued for 4 h to obtain a flame-retardant thermal-insulation polyurethane material;

[0084] The mass ratio of the polyether polyol, the flame-retardant filler, the modified epoxy resin, the catalyst, the foaming agent, the foam stabilizer, and the polymethylene polyphenyl polyisocyanate is 100:5:9:3.5:3.8:0.8:115.

[0085] Example 4

[0086] The embodiment discloses a preparation method of a flame-retardant thermal-insulation polyurethane material, and comprises the following steps:

[0087] In step (1), expandable perlite, γ-aminopropyl triethoxysilane, ethanol, and water are mixed at a mass ratio of 1:1:20:1, ultrasonic dispersion is performed for 20 min, stirring reaction is performed at a temperature of 80℃ for 3 h, after the reaction is completed, filtration is performed, the filter cake is taken out, water with a mass 10 times that of the filter cake is added for washing, and drying is performed at a temperature of 60℃ for 24 h to obtain amino expandable perlite.

[0088] In step (2), melamine, polyformaldehyde, and water are mixed and dissolved, triethylamine is added to adjust the pH value to 9, stirring reaction is performed at a temperature of 65℃ for 2 h, after the reaction is completed, a 35wt% diethanolamine aqueous solution is added dropwise, the dropwise adding time is 20 min, after the dropwise adding is completed, reaction is continued at a temperature of 65℃ for 3 h, after the reaction is completed, triethylamine and water are removed by rotary evaporation to obtain a flame retardant.

[0089] The mass ratio of the amino expandable perlite, N,N-dimethylformamide, dimethyl chlorophosphate, and triethylamine is 10:220:8:9.2.

[0090] In step (2), melamine, polyformaldehyde, and water are mixed and dissolved, triethylamine is added to adjust the pH value to 9, stirring reaction is performed at a temperature of 65℃ for 2 h, after the reaction is completed, a 35wt% diethanolamine aqueous solution is added dropwise, the dropwise adding time is 20 min, after the dropwise adding is completed, reaction is continued at a temperature of 65℃ for 3 h, after the reaction is completed, triethylamine and water are removed by rotary evaporation to obtain a flame retardant.

[0091] The mass ratio of the melamine, the polyformaldehyde, the water, and the 35wt% diethanolamine aqueous solution is 12.6:9.5:200:31.

[0092] The phosphate-modified expanded perlite, the flame retardant, sodium hydroxide, N,N-dimethylformamide are mixed in a mass ratio of 10:30:1.3:120, and reacted at a set temperature of 160℃ for 18h. After the reaction is completed, filtration is performed, the filter cake is taken, 10 times the amount of ethanol is added to wash the filter cake, and drying is performed at a temperature of 60℃ for 12h to obtain a flame retardant / expanded perlite composite material. The flame retardant / expanded perlite composite material is mixed with graphene in a mass ratio of 10:1 to obtain a flame-retardant filler;

[0093] Step (3), the polyether polyol, the flame-retardant filler, the modified epoxy resin, the catalyst, the foaming agent, and the foam stabilizer are mixed and stirred at a rotation speed of 4000r / min for 30min to obtain A material;

[0094] The foaming agent is water; the catalyst is a compound of 2-ethyl-4-methylimidazole, 2,4,6-tris(dimethylaminomethyl)phenol, and triethylenediamine in a mass ratio of 2.5:0.45:0.7;

[0095] The modified epoxy resin is prepared by the following steps:

[0096] The trimethylolpropane triglycidyl ether and the binaphthol are uniformly mixed in a molar ratio of 2.8:1 in a nitrogen atmosphere at a temperature of 100℃. Tetrabutylammonium bromide is added, and the temperature is raised to 120℃ for 2h. After the reaction is completed, ethyl triphenylphosphonium bromide is added, and the temperature is raised to 150℃ at a rate of 1℃ / min for 2h. After the reaction is completed, the temperature is cooled to room temperature to obtain a hyperbranched epoxy resin. The hyperbranched epoxy resin is mixed with epoxy resin E51 in a mass ratio of 9:91 to obtain a modified epoxy resin. The mass sum of tetrabutylammonium bromide and ethyl triphenylphosphonium bromide is 0.06% of the mass sum of trimethylolpropane triglycidyl ether and binaphthol. The mass ratio of tetrabutylammonium bromide to ethyl triphenylphosphonium bromide is 1.6:1.

[0097] The B material polymethylene polyphenyl polyisocyanate is added to the A material and uniformly mixed by stirring at a rotation speed of 4000r / min for 20s to obtain a polyurethane-based glue. The polyurethane-based glue is placed in a mold and cured at a temperature of 120℃ for 1h. After the mold is opened, curing is continued for 4h to obtain a flame-retardant thermal insulation polyurethane material.

[0098] The mass ratio of the polyether polyol, the flame-retardant filler, the modified epoxy resin, the catalyst, the foaming agent, the foam stabilizer, and the polymethylene polyphenyl polyisocyanate is 100:6:10:4:4:1:120.

[0099] Example 5

[0100] The present embodiment discloses a preparation method of a flame-retardant thermal insulation polyurethane edge sealing sandwich panel, which comprises the following steps:

[0101] The materials of each layer were combined in the order of upper panel, core layer, and lower panel, edge sealing was performed using polyurethane-based glue, and curing was performed at a temperature of 120 DEG C for 5h to obtain a flame-retardant thermal insulation polyurethane edge-sealed sandwich panel.

[0102] The polyurethane-based glue was the polyurethane-based glue prepared in Examples 1-4, and the obtained flame-retardant thermal insulation polyurethane edge-sealed sandwich panels were respectively denoted as samples 1-4.

[0103] Comparative Example 1

[0104] The present comparative example discloses a preparation method of a polyurethane material, comprising the following steps:

[0105] Step (1), expand perlite, gamma-aminopropyl triethoxysilane, ethanol, and water were mixed in a mass ratio of 1:0.8:15:1, ultrasonic dispersion was performed for 10 min, stirring reaction was performed at a temperature of 70 DEG C for 4h, after the reaction was completed, filtration was performed, the filter cake was taken, the filter cake was washed with water in an amount of 10 times the mass of the filter cake, and drying was performed at a temperature of 50 DEG C for 24h to obtain amino expand perlite;

[0106] The amino expand perlite and N,N-dimethylformamide were mixed, ultrasonic dispersion was performed for 10 min, dimethyl chlorophosphate and triethylamine were added, reaction was performed at a temperature of 20 DEG C for 30h, after the reaction was completed, filtration was performed, the filter cake was taken, the filter cake was washed with ethanol in an amount of 10 times the mass of the filter cake, and drying was performed at a temperature of 50 DEG C for 24h to obtain phosphate ester modified expand perlite;

[0107] The mass ratio of the amino expand perlite, N,N-dimethylformamide, dimethyl chlorophosphate, and triethylamine was 10:190:7.5:8.8;

[0108] The phosphate ester modified expand perlite and graphene were mixed in a mass ratio of 10:1 to obtain a flame-retardant filler;

[0109] Step (3), polyether polyol, flame-retardant filler, modified epoxy resin, catalyst, foaming agent, and bubble uniformizing agent were mixed, stirring was performed at a rotation speed of 4000r / min for 30 min to obtain A material;

[0110] The foaming agent was water; the catalyst was a compound of 2-ethyl-4-methylimidazole, 2,4,6-tris(dimethylaminomethyl)phenol, and triethylenediamine in a mass ratio of 2:0.45:1;

[0111] The modified epoxy resin was prepared by the following steps:

[0112] Mixing trimethylolpropane triglycidyl ether and binaphthyl in a molar ratio of 2.7:1 under a nitrogen atmosphere at a temperature of 100℃, adding tetrabutylammonium bromide, and increasing the temperature to 110℃ for 3h of reaction; after the reaction is completed, adding ethyl triphenylphosphonium bromide, and increasing the temperature to 140℃ at a rate of 1℃ / min for 2.5h of continued reaction; after the reaction is completed, cooling to room temperature to obtain a hyperbranched epoxy resin; mixing the hyperbranched epoxy resin with epoxy resin E51 in a mass ratio of 7:93 to obtain a modified epoxy resin; wherein the mass sum of tetrabutylammonium bromide and ethyl triphenylphosphonium bromide is 0.06% of the mass sum of trimethylolpropane triglycidyl ether and binaphthyl; and the mass ratio of tetrabutylammonium bromide to ethyl triphenylphosphonium bromide is 1.6:1;

[0113] Adding the B material polymethylene polyphenyl polyisocyanate to the A material, stirring at a speed of 4000r / min for 20s to mix uniformly, and obtaining a polyurethane-based glue; placing the polyurethane-based glue in a mold, curing at a temperature of 120℃ for 1h, continuing to cure for 4h after demolding, and obtaining a polyurethane material;

[0114] The mass ratio of the polyether polyol, the flame-retardant filler, the modified epoxy resin, the catalyst, the foaming agent, the foam stabilizer, and the polymethylene polyphenyl polyisocyanate is 100:4:8:3:3.5:0.5:110.

[0115] Comparative Example 2

[0116] This comparative example discloses a preparation method of a polyurethane material, including the following steps:

[0117] Step (1), mixing expanded perlite, γ-aminopropyltriethoxysilane, ethanol, and water in a mass ratio of 1:0.8:15:1, ultrasonic dispersion for 10min, stirring and reacting at a temperature of 70℃ for 4h, after the reaction is completed, filtering, taking the filter cake, washing with water in an amount of 10 times the mass of the filter cake, and drying at a temperature of 50℃ for 24h to obtain amino expanded perlite;

[0118] Mixing the amino expanded perlite and N,N-dimethylformamide, ultrasonic dispersion for 10min, adding dimethyl chlorophosphate and triethylamine, and reacting at a temperature of 20℃ for 30h; after the reaction is completed, filtering, taking the filter cake, washing with ethanol in an amount of 10 times the mass of the filter cake, and drying at a temperature of 50℃ for 24h to obtain phosphate ester modified expanded perlite;

[0119] The mass ratio of the amino expanded perlite, N,N-dimethylformamide, dimethyl chlorophosphate, and triethylamine is 10:190:7.5:8.8.

[0120] Step (2), mixing and dissolving melamine, paraformaldehyde and water, adding triethylamine to adjust the pH value to 8.5, stirring and reacting at 60℃ for 2.5h, after the reaction is completed, adding 35wt% diethanolamine aqueous solution dropwise, the dropwise adding time is 10min, after the dropwise adding is completed, continuing to react at 60℃ for 3h, after the reaction is completed, removing triethylamine and water by rotary evaporation to obtain the flame retardant;

[0121] The mass ratio of melamine, paraformaldehyde, water and 35wt% diethanolamine aqueous solution is 12.6:9:180:30.7.

[0122] Mixing the phosphate modified expanded perlite, the flame retardant, sodium hydroxide and N,N-dimethylformamide in a mass ratio of 8:28:1.2:100, reacting at a set temperature of 150℃ for 18h, after the reaction is completed, filtering, taking the filter cake, washing the filter cake with 10 times the amount of ethanol, and drying at 50℃ for 12h to obtain the flame retardant / expanded perlite composite material; mixing the flame retardant / expanded perlite composite material and graphene in a mass ratio of 10:1 to obtain the flame retardant filler;

[0123] Step (3), mixing the polyether polyol, the flame retardant filler, the catalyst, the foaming agent and the foam stabilizer, stirring at a speed of 4000r / min for 30min to obtain A material;

[0124] The foaming agent is water; the catalyst is a compound of 2-ethyl-4-methylimidazole, 2,4,6-tris(dimethylaminomethyl)phenol and triethylenediamine in a mass ratio of 2:0.45:1.

[0125] Adding the polyurethane-based adhesive to A material and stirring at a speed of 4000r / min for 20s to mix uniformly to obtain a polyurethane-based adhesive; placing the polyurethane-based adhesive in a mold and curing at 120℃ for 1h, continuing to cure for 4h after demolding to obtain a polyurethane material.

[0126] The mass ratio of the polyether polyol, the flame retardant filler, the catalyst, the foaming agent, the foam stabilizer and the polymeric methylene polyphenyl polyisocyanate is 100:4:3:3.5:0.5:110.

[0127] Comparative Example 3

[0128] The present comparative example discloses a preparation method of a polyurethane edge-sealed sandwich panel, comprising the following steps:

[0129] Assembling the materials in the order of the upper panel, the core layer and the lower panel, using the polyurethane-based adhesive to seal the edges, and curing at 120℃ for 5h to obtain a flame-retardant thermal-insulation polyurethane edge-sealed sandwich panel.

[0130] The polyurethane-based adhesive is the polyurethane-based adhesive prepared in Comparative Examples 1-2, and the prepared polyurethane edge-sealed sandwich panels are respectively denoted as Samples 5-6.

[0131] In the above examples and comparative examples: the expanded perlite is commercially available, with a bulk density of 117 kg / m 3 , the dimethyl chlorophosphate is from Macklin Biochemical Technology Co., Ltd., with a CAS number of 813-77-4, the graphene is from Aladdin Biochemical Technology Co., Ltd., with a product number of G302113, the polyether polyol is of TMN-450 type, the dinaphthalene diol is from Macklin Biochemical Technology Co., Ltd., with a CAS number of 602-09-5, the polymethylene polyphenyl polyisocyanate is of PM-200 type, the cell stabilizer is from Demosyn, with a product number of AK-8805, and the core layer is a commercially available rock wool insulation board with a thickness of 0.6 mm, and the upper and lower face plates are both color-coated steel plates with a thickness of 0.8 mm.

[0132] Test examples

[0133] The polyurethane materials prepared in Examples 1-4 and Comparative Examples 1-2 are subjected to performance tests, and the specific test results are shown in Table 1; the Samples 1-6 prepared in Example 5 and Comparative Example 3 are subjected to comprehensive performance tests, and the specific test results are shown in Table 2:

[0134] Table 1

[0135]

[0136]

[0137] Table 2

[0138] Thermal conductivity (W / m-K) Limiting oxygen index (%) Sample 1 ＜0.02 32 Sample 2 ＜0.02 32 Sample 3 ＜0.02 33 Sample 4 ＜0.02 33 Sample 5 ＜0.02 30 Sample 6 ＜0.02 32

[0139] The detection of each index in Table 1 and Table 2 is respectively based on the following standards: the density is determined with reference to GB / T6343 “Determination of apparent (volume) density of foamed plastics box rubber”; the compressive strength is determined with reference to GB / T1448 “Glass fiber reinforced plastic compression performance test method”; the thermal conductivity is determined with reference to GB / T10297 “Determination of thermal conductivity of non-metallic solid materials”; the limiting oxygen index is determined with reference to GB / T8624-1997 “Classification of building materials and products based on combustion performance”; and the dimensional stability is determined with reference to GB / T8811 “Hard foam plastic dimensional stability test method”, with a temperature range of 70°C to -30°C and a test time of 48 h.

[0140] The phosphonate-modified expanded perlite in Comparative Example 1 does not react with the flame retardant, lacks the effect of the organic flame retardant component on improving the flame retardant properties of the material, and has decreased dispersibility and compatibility, so the polyurethane material prepared in Comparative Example 1 has decreased compressive strength and decreased limiting oxygen index, and the sample 5 prepared in Comparative Example 1 has decreased flame retardant properties.

[0141] Comparative Example 2 lacks the addition of the modified epoxy resin, lacks the reaction of the epoxy groups with the isocyanate groups to form heat-resistant groups during the curing process, and lacks the effect of the crosslinking points on improving the mechanical properties of the material, so the dimensional stability and the compressive strength of Comparative Example 2 are decreased.

[0142] Although embodiments of the present application have been shown and described, it is to be understood that various modifications, substitutions, replacements and changes can be made to these embodiments without departing from the principles and spirit of the present application, and the scope of the present application is defined by the appended claims and their equivalents.

Claims

1. A process for the production of a flame-retardant, thermally insulated polyurethane edge-banded sandwich panel, characterized in that, Comprising the following steps: Step one, polyether polyol, flame retardant filler, modified epoxy resin, catalyst, foaming agent, foam stabilizer are mixed, stirred, to get A material; B material multi-methylene polyphenyl polyisocyanate is added into A material, stirred at 4000-5000r / min for 20s, mixed uniformly, to get polyurethane-based glue; The mass ratio of polyether polyol, flame retardant filler, modified epoxy resin, catalyst, foaming agent, foam stabilizer, multi-methylene polyphenyl polyisocyanate is 100:4-6:8-10:3-4:3.5-4:0.5-1:110-120; The flame retardant filler is prepared by the following steps: Step (1), the expanded perlite, gamma-aminopropyl triethoxysilane, ethanol, water are mixed, ultrasonic dispersion, reaction, after the reaction, filtration, washing, drying, to get amino expanded perlite; The amino expanded perlite, N,N-dimethylformamide are mixed, ultrasonic dispersion, add dimethyl chlorophosphate, triethylamine, reaction, after the reaction, filtration, washing, drying, to get phosphate ester modified expanded perlite; Step (2), melamine, paraformaldehyde, water are mixed and dissolved, add regulator to adjust pH value, reaction, after the reaction, drop in diethanolamine aqueous solution, after drop, continue to react, after the reaction, rotary evaporation, to get flame retardant; The phosphate ester modified expanded perlite, flame retardant, sodium hydroxide, N,N-dimethylformamide are mixed, reaction, after the reaction, filtration, washing, drying, to get flame retardant / expanded perlite composite material; The flame retardant / expanded perlite composite material is mixed with graphene, to get flame retardant filler; The modified epoxy resin is prepared by the following steps: The trimethylolpropane triglycidyl ether, binaphthol are mixed uniformly in nitrogen atmosphere at 100℃, add tetrabutylammonium bromide, react in nitrogen atmosphere at 110-120℃ for 2-3h, after the reaction, add ethyl triphenylphosphonium bromide, again heat to 140-150℃ at the rate of 1℃ / min, continue to react for 2-2.5h, after the reaction, cool to room temperature, to get hyperbranched epoxy resin; The hyperbranched epoxy resin is mixed with epoxy resin E51 at the mass ratio of 7-9:91-93, to get modified epoxy resin; The mass sum of tetrabutylammonium bromide and ethyl triphenylphosphonium bromide is 0.06-0.08% of the mass sum of trimethylolpropane triglycidyl ether and binaphthol; The mass ratio of tetrabutylammonium bromide and ethyl triphenylphosphonium bromide is 1.6:1; Step two, the materials of each layer are combined in the order of upper panel, sandwich layer, lower panel, edge sealing is carried out by using polyurethane-based glue, curing, to get flame retardant thermal insulation polyurethane edge sealing sandwich panel.

2. The method for preparing a flame-retardant and heat-insulating polyurethane edge-sealed sandwich panel according to claim 1, characterized in that, In step one: the foaming agent is water; the catalyst is 2-ethyl-4-methylimidazole, 2,4,6-tris(dimethylaminomethyl)phenol, triethylenediamine, compounded at the mass ratio of 2-2.5:0.45:0.7-1; during the preparation of A material, the stirring condition is: stirring at 4000-5000r / min for 20-30min.

3. The method for preparing a flame-retardant and heat-insulating polyurethane edge-sealed sandwich panel according to claim 1, characterized in that, In the preparation of the flame-retardant filler in step one, step (1) is: In the preparation of the amino expanded perlite: the mass ratio of expanded perlite, γ-aminopropyltriethoxysilane, ethanol and water is 1:0.8-1:15-20:1; the reaction condition is: stirring reaction at 70-80℃ for 3-4h; In the preparation of the phosphate ester modified expanded perlite: the mass ratio of amino expanded perlite, N,N-dimethylformamide, dimethyl chlorophosphate and triethylamine is 10:190-220:7.5-8:8.8-9.2; the reaction condition is: reaction at 20-30℃ for 24-30h.

4. The method for preparing a flame-retardant and heat-insulating polyurethane edge-sealed sandwich panel according to claim 1, characterized in that, In the preparation of the flame-retardant filler in step one, step (2) is: In the preparation of the flame retardant: the mass ratio of melamine, paraformaldehyde, water and diethanolamine aqueous solution is 12.6:9-9.5:180-200:30.7-31; the diethanolamine aqueous solution is 35wt% diethanolamine aqueous solution, the dropping time is 10-20min; the reaction condition is: stirring reaction at 60-65℃ for 2-2.5h at pH 8.5-9, the continuous reaction condition is: continuous reaction at 60-65℃ for 3h; In the preparation of the flame retardant / expanded perlite composite material: the mass ratio of phosphate ester modified expanded perlite, flame retardant, sodium hydroxide and N,N-dimethylformamide is 8-10:28-30:1.2-1.3:100-120; the reaction condition is: reaction at a set temperature of 150-160℃ for 18h; In the preparation of the flame-retardant filler: the mass ratio of the flame retardant / expanded perlite composite material and graphene is 10:1-1.

5.

5. The method for preparing a flame-retardant and heat-insulating polyurethane edge-sealed sandwich panel according to claim 1, characterized in that, In the step two: the curing condition is: curing at 120℃ for 4-5h.

6. A flame-retardant thermal insulation polyurethane edge-banded sandwich panel prepared by the method according to any one of claims 1-5.

7. The use of the flame-retardant thermal insulation polyurethane edge-banded sandwich panel according to claim 6 in the field of industrial upgrading and green building.

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