Mechanical foaming material for thermal insulation and reinforcement of external wall and preparation method of mechanical foaming material

Abstract

The invention relates to the technical field of foaming materials, and discloses a mechanical foaming material for external wall thermal insulation and reinforcement and a preparation method thereof.The mechanical foaming material is prepared from raw materials including 2-vinyl propane-1, 3-diol, diphenyl chlorophosphate, aminopropyltriethoxysilane, nano-silica and the like through a series of reactions. The phosphorus-containing modified nano silicon dioxide is prepared. And adding deionized water, phosphorus-containing modified nano silicon dioxide, a curing agent and other raw materials into the epoxy resin, and carrying out mechanical stirring foaming, injection molding and drying to obtain the mechanical foaming material. The flame retardant property of the mechanical foaming material is improved by utilizing the nano silicon dioxide and the flame retardant elements, and the mechanical property of the mechanical foaming material is improved by utilizing the nano silicon dioxide and the polypropylene fibers. The mechanical foaming material prepared by the invention has excellent flame retardant property and mechanical property.

Description

Technical Field

[0001] The invention relates to the technical field of foaming materials, in particular to a mechanical foaming material for exterior wall thermal insulation reinforcement and a preparation method thereof. Background Art

[0002] Every year, building energy consumption will cause a lot of energy waste. Under the current trend of energy conservation and environmental protection, building insulation materials play a vital role in building energy conservation and are of great significance to protecting the environment and achieving sustainable development.

[0003] The existing ones generally use epoxy resin materials combined with dry powder materials. Epoxy resin foaming materials have the advantages of light weight, and dry powder materials are fire-resistant. The two components of epoxy resin and dry powder materials are resistant to high temperatures and have strong weather resistance.

[0004] Epoxy resin is an important thermosetting resin. After curing, it has low shrinkage and water absorption, high bonding strength and mechanical strength. Therefore, it is widely used in organic thermal insulation materials. However, although the organic thermal insulation material prepared from epoxy resin is light in weight and has good thermal insulation performance, it has a serious flammability defect, which is not conducive to the use of epoxy resin thermal insulation materials. Therefore, it is necessary to improve the flame retardant properties of epoxy resin to expand its practical application range.

[0005] For example, the patent application number 202321488676.0 discloses a bonding anchor combined with grouting insulation nail, but it cannot improve the flame retardant properties of building insulation materials. Based on this, the present invention prepares a mechanical foaming material using water-based epoxy resin E44 as a raw material, which has excellent flame retardant properties and mechanical properties. Summary of the invention

[0006] 1. Technical issues to be resolved

[0007] In view of the deficiencies in the prior art, the present invention provides a mechanical foaming material for exterior wall thermal insulation reinforcement and a preparation method thereof. The prepared mechanical foaming material has good flame retardant properties and mechanical properties.

[0008] (II) Technical solution

[0009] A mechanical foaming material for exterior wall thermal insulation reinforcement, the mechanical foaming material is composed of the following components in parts by weight: 100 parts of epoxy resin, 1-5 parts of deionized water, 1-5 parts of phosphorus-modified nano-silicon dioxide, 1-3 parts of polyethylene fiber, 5-20 parts of curing agent, and 0.2-0.8 parts of surfactant;

[0010] The preparation method of the mechanical foaming material is:

[0011] Add epoxy resin into a flask, then add deionized water, phosphorus-modified nano-silica, and polyethylene fiber, use a high-speed disperser to stir at a speed of 1500r / min for 10-20min, cool to room temperature, then add a curing agent and a surfactant to perform mechanical stirring and foaming, finally inject into a mold for molding, leave at room temperature for 24h, demold, and dry to obtain a mechanical foaming material.

[0012] Furthermore, the curing agent is selected from any one of N-aminoethylpiperazine and diethylenetriamine; the surfactant is selected from any one of surfactant AMPHITOL 24B and surfactant EMAL TD.

[0013] Furthermore, the preparation method of the phosphorus-modified nano-silicon dioxide is:

[0014] (1) Under ice bath conditions, 2-vinylpropane-1,3-diol and triethylamine are added to a dichloromethane solvent, stirred and mixed, and then diphenyl chlorophosphate is added thereto, stirred and reacted for 1-2 hours, and then the temperature is raised to room temperature and the reaction is continued for 6-12 hours. After the reaction is completed, the mixture is washed with deionized water and saturated brine in sequence, dried, and rotary evaporated to obtain an intermediate 1, wherein the mass ratio of 2-vinylpropane-1,3-diol, triethylamine, and diphenyl chlorophosphate is 1:2-2.5:5-5.8.

[0015] (2) In an ice bath, aminopropyl triethoxysilane and 4-methoxyphenol polymerization inhibitor are added to a toluene solvent, stirred and dispersed, and then intermediate 1 is added thereto, stirred and reacted for 20-40 minutes, heated to 25-40°C, and continued to react for 5-10 hours. After the reaction is completed, the mixture is washed with deionized water, rotary evaporated, and dried to obtain intermediate 2, wherein the mass ratio of aminopropyl triethoxysilane to intermediate 1 is 1:5-6, and the amount of the polymerization inhibitor is 4-8% of the total mass of aminopropyl triethoxysilane and intermediate 1.

[0016] (3) Under a nitrogen atmosphere, add nano-silica and intermediate 2 to a toluene solvent, raise the temperature to 100-110° C., and stir to react for 8-12 hours. After the reaction is completed, filter, wash with toluene, and dry to obtain phosphorus-modified nano-silica, wherein the mass ratio of nano-silica to intermediate 2 is 1:0.25-0.8.

[0017] 3. Beneficial technical effects

[0018] The present invention uses 2-vinyl propane-1,3-diol to react with diphenyl chlorophosphate under the catalysis of triethylamine to obtain intermediate 1, and then reacts the intermediate with aminopropyl triethoxysilane to obtain intermediate 2. Intermediate 2 is used to modify the surface of nano silicon dioxide to obtain phosphorus-modified nano silicon dioxide, which has a novel structure and a relatively simple preparation method. Finally, epoxy resin is used as a base resin, deionized water and a surfactant are used as a foaming agent, phosphorus-modified nano silicon dioxide is used as a filler, and polyethylene fiber is used as a reinforcing phase, mechanical stirring and foaming are performed, injection molding is performed, and drying is performed to obtain a mechanical foaming material.

[0019] The mechanical foaming material prepared by the present invention contains phosphorus, nitrogen and silicon, all of which are flame retardant elements. The phosphorus element generates strong dehydrating substances such as phosphoric acid and metaphosphoric acid when heated to promote the dehydration of the material into carbon, forming a dense carbon layer on the surface of the material to isolate material transportation and energy transfer; the silicon element generates a glass-like substance when heated, covering the surface of the material, further isolating material transportation and energy transfer, and the nitrogen element generates flame-retardant gas when heated to dilute the content of flammable gas in the air, further improving the flame retardant properties of the material. In addition, the nano-silicon dioxide as an inorganic nanoparticle can form an organic-inorganic synergistic flame retardant system with organic flame retardant elements to jointly improve the flame retardant properties of the material.

[0020] The present invention uses polyethylene fiber as a reinforcing phase, and after mechanical stirring and foaming, it can be evenly dispersed in the system. When subjected to external force, it can effectively transfer the load and improve the mechanical properties of the material. Nano silicon dioxide itself is easy to agglomerate, and the present invention makes it organic to enhance its dispersion in the system. Nano silicon dioxide can not only serve as a stress concentration point, but also absorb energy when subjected to external force impact, thereby improving the mechanical properties of the material. Moreover, the addition of nano silicon dioxide can increase the viscosity of the material, increase the resistance of the gas expansion and growth inside the system, and reduce the number of pores, thereby improving the mechanical properties of the material. The present invention uses a surfactant and deionized water as a foaming agent to improve the foaming ability of the epoxy resin and help form uniform and stable pores. The mechanical foaming material prepared by the present invention has excellent flame retardant properties and mechanical properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 It is the reaction route for phosphorus-modified nano-silica.

[0022] Figure 2 This is the super depth of field image of Example 1. DETAILED DESCRIPTION

[0023] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. 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.

[0024] Example 1

[0025] (1) In an ice bath, 10 g of 2-vinylpropane-1,3-diol and 20 g of triethylamine were added to a dichloromethane solvent and stirred to mix. Then, 58 g of diphenyl chlorophosphate was added thereto and stirred to react for 1.5 h. The mixture was then heated to room temperature and continued to react for 10 h. After the reaction was completed, the mixture was washed with deionized water and saturated brine in sequence, dried, and rotary evaporated to obtain intermediate 1.

[0026] (2) In an ice bath, 10 g of aminopropyltriethoxysilane and 2.8 g of 4-methoxyphenol inhibitor were added to toluene solvent and dispersed with stirring. Then, 60 g of intermediate 1 was added thereto and stirred for reaction for 30 min. The temperature was raised to 30°C and the reaction was continued for 8 h. After the reaction was completed, the mixture was washed with deionized water, rotary evaporated and dried to obtain intermediate 2.

[0027] (3) Under a nitrogen atmosphere, 20 g of nano-silica and 15 g of intermediate 2 were added to a toluene solvent, the temperature was raised to 105° C., and the mixture was stirred for reaction for 9 h. After the reaction was completed, the mixture was filtered, washed with toluene, and dried to obtain phosphorus-modified nano-silica.

[0028] (4) Add 100 g of epoxy resin E-44 into a flask, then add 1 g of deionized water, 1 g of phosphorus-modified nano-silica, and 1 g of polyethylene fiber, stir for 20 min at 1500 r / min using a high-speed disperser, cool to room temperature, then add 5 g of diethylenetriamine curing agent and 0.8 g of surfactant EMAL TD for mechanical stirring and foaming, finally inject into a mold for molding, leave at room temperature for 24 h, demold, and dry to obtain a mechanically foamed material.

[0029] Example 2

[0030] (1) In an ice bath, 10 g of 2-vinylpropane-1,3-diol and 25 g of triethylamine were added to a dichloromethane solvent and stirred to mix. Then, 55 g of diphenyl chlorophosphate was added thereto and stirred to react for 2 h. The mixture was then heated to room temperature and continued to react for 6 h. After the reaction was completed, the mixture was washed with deionized water and saturated brine in sequence, dried, and rotary evaporated to obtain intermediate 1.

[0031] (2) In an ice bath, 10 g of aminopropyltriethoxysilane and 4.2 g of 4-methoxyphenol inhibitor were added to toluene solvent and dispersed with stirring. Then, 50% of intermediate 1 was added thereto and stirred for reaction for 40 min. The temperature was raised to 30°C and the reaction was continued for 10 h. After the reaction was completed, the mixture was washed with deionized water, rotary evaporated and dried to obtain intermediate 2.

[0032] (3) Under a nitrogen atmosphere, 20 g of nano-silica and 10 g of intermediate 2 were added to a toluene solvent, the temperature was raised to 105° C., and the reaction was stirred for 10 h. After the reaction was completed, the solution was filtered, washed with toluene, and dried to obtain phosphorus-modified nano-silica.

[0033] (4) Add 100 g of epoxy resin E-44 into a flask, then add 3 g of deionized water, 2 g of phosphorus-modified nano-silica, and 1.5 g of polyethylene fiber, stir for 20 min at 1500 r / min using a high-speed disperser, cool to room temperature, then add 10 g of diethylenetriamine curing agent and 0.2 g of surfactant AMPHITOL 24B to perform mechanical stirring and foaming, finally inject into a mold for molding, leave at room temperature for 24 h, demold, and dry to obtain a mechanically foamed material.

[0034] Example 3

[0035] (1) In an ice bath, 10 g of 2-vinylpropane-1,3-diol and 22 g of triethylamine were added to a dichloromethane solvent and stirred to mix. Then, 50 g of diphenyl chlorophosphate was added thereto and stirred to react for 1 h. The mixture was then heated to room temperature and continued to react for 12 h. After the reaction was completed, the mixture was washed with deionized water and saturated brine in sequence, dried, and rotary evaporated to obtain intermediate 1.

[0036] (2) In an ice bath, 10 g of aminopropyltriethoxysilane and 5.6 g of 4-methoxyphenol polymerization inhibitor were added to toluene solvent and dispersed with stirring. Then, 56 g of intermediate 1 was added thereto and stirred for reaction for 30 min. The temperature was raised to 30°C and the reaction was continued for 6 h. After the reaction was completed, the mixture was washed with deionized water, rotary evaporated and dried to obtain intermediate 2.

[0037] (3) Under a nitrogen atmosphere, 20 g of nano-silica and 5 g of intermediate 2 were added to a toluene solvent, the temperature was raised to 105° C., and the mixture was stirred for reaction for 10 h. After the reaction was completed, the mixture was filtered, washed with toluene, and dried to obtain phosphorus-modified nano-silica.

[0038] (4) Add 100 g of epoxy resin E-44 into a flask, then add 5 g of deionized water, 3 g of phosphorus-modified nano-silica, and 2 g of polyethylene fiber, use a high-speed disperser to stir at a speed of 1500 r / min for 10 min, cool to room temperature, then add 20 g of N-aminoethylpiperazine curing agent and 0.5 g of surfactant EMAL TD for mechanical stirring and foaming, finally inject into a mold for molding, leave at room temperature for 24 h, demold, and dry to obtain a mechanically foamed material.

[0039] Example 4

[0040] (1) In an ice bath, 10 g of 2-vinylpropane-1,3-diol and 24 g of triethylamine were added to a dichloromethane solvent and stirred to mix. Then, 55 g of diphenyl chlorophosphate was added thereto and stirred to react for 1 h. The mixture was then heated to room temperature and continued to react for 8 h. After the reaction was completed, the mixture was washed with deionized water and saturated brine in sequence, dried, and rotary evaporated to obtain intermediate 1.

[0041] (2) In an ice bath, 10 g of aminopropyltriethoxysilane and 4 g of 4-methoxyphenol inhibitor were added to toluene solvent and dispersed with stirring. Then, 56 g of intermediate 1 was added thereto and stirred for reaction for 40 min. The temperature was raised to 25°C and the reaction was continued for 10 h. After the reaction was completed, the mixture was washed with deionized water, rotary evaporated and dried to obtain intermediate 2.

[0042] (3) Under a nitrogen atmosphere, 20 g of nano-silica and 10 g of intermediate 2 were added to a toluene solvent, the temperature was raised to 110° C., and the mixture was stirred for reaction for 8 h. After the reaction was completed, the mixture was filtered, washed with toluene, and dried to obtain phosphorus-modified nano-silica.

[0043] (4) Add 100 g of epoxy resin E-44 into a flask, then add 5 g of deionized water, 4 g of phosphorus-modified nano-silica, and 2.5 g of polyethylene fiber, use a high-speed disperser to stir at a speed of 1500 r / min for 20 min, cool to room temperature, then add 15 g of N-aminoethylpiperazine curing agent and 0.5 g of surfactant EMAL TD for mechanical stirring and foaming, finally inject into a mold for molding, leave at room temperature for 24 h, demold, and dry to obtain a mechanically foamed material.

[0044] Example 5

[0045] (1) In an ice bath, 10 g of 2-vinylpropane-1,3-diol and 25 g of triethylamine were added to a dichloromethane solvent and stirred to mix. Then, 58 g of diphenyl chlorophosphate was added thereto and stirred to react for 1 h. The mixture was then heated to room temperature and continued to react for 10 h. After the reaction was completed, the mixture was washed with deionized water and saturated brine in sequence, dried, and rotary evaporated to obtain intermediate 1.

[0046] (2) In an ice bath, 10 g of aminopropyltriethoxysilane and 2.4 g of 4-methoxyphenol inhibitor were added to toluene solvent and dispersed with stirring. Then, 56 g of intermediate 1 was added thereto and stirred for reaction for 20 min. The temperature was raised to 40°C and the reaction was continued for 5 h. After the reaction was completed, the mixture was washed with deionized water, rotary evaporated and dried to obtain intermediate 2.

[0047] (3) Under a nitrogen atmosphere, 20 g of nano-silica and 16 g of intermediate 2 were added to a toluene solvent, the temperature was raised to 100° C., and the mixture was stirred for reaction for 12 h. After the reaction was completed, the mixture was filtered, washed with toluene, and dried to obtain phosphorus-modified nano-silica.

[0048] (4) Add 100 g of epoxy resin E-44 into a flask, then add 4 g of deionized water, 5 g of phosphorus-modified nano-silica, and 3 g of polyethylene fiber, stir for 15 min at 1500 r / min using a high-speed disperser, cool to room temperature, then add 16 g of diethylenetriamine curing agent and 0.6 g of surfactant AMPHITOL 24B to perform mechanical stirring and foaming, finally inject into a mold for molding, leave at room temperature for 24 h, demold, and dry to obtain a mechanically foamed material.

[0049] Comparative Example 1

[0050] The difference between this comparative example and Example 1 is that step (4) does not contain phosphorus-modified nano-silicon dioxide, and the remaining steps and raw materials are the same as those of Example 1.

[0051] The fire resistance performance of the material is tested in accordance with the international standard GB / T8333.

[0052] Table 1:

[0053] Fire resistance Example 1 Class A non-flammable Example 2 Class A non-flammable Example 3 Class A non-flammable Example 4 Class A non-flammable Example 5 Class A non-flammable Comparative Example 1 Class B flammable

[0054] It can be seen from the table that the mechanical foaming material prepared by the present invention has good fire retardant properties.

[0055] According to the national standard GB / 5486-2008, the mechanical properties of the materials were tested using a universal material testing machine.

[0056] Table 2:

[0057] Compressive strength (MPa) Example 1 0.768 Example 2 0.842 Example 3 0.982 Example 4 0.950 Example 5 0.894 Comparative Example 1 0.527

[0058] It can be seen from the table that the mechanical foaming material prepared by the present invention has excellent mechanical properties.

[0059] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the invention or exceed the scope defined by the claims, they shall all fall within the protection scope of the present invention.

Claims

1. A mechanical foaming material for exterior wall thermal insulation reinforcement, characterized in that: The mechanical foaming material is composed of the following components in parts by weight: Composition: 100 parts of epoxy resin, 1-5 parts of deionized water, 1-5 parts of phosphorus-modified nano-silicon dioxide, 1-3 parts of polyethylene fiber, 5-20 parts of curing agent, 0.2-0.8 parts of surfactant; The preparation method of the mechanical foaming material is: Add epoxy resin into a flask, then add deionized water, phosphorus-modified nano-silica, and polyethylene fiber, use a high-speed disperser to stir at a speed of 1500r / min for 10-20min, cool to room temperature, then add a curing agent and a surfactant to perform mechanical stirring and foaming, finally inject into a mold for molding, leave at room temperature for 24h, demold, and dry to obtain a mechanical foaming material.

2. The mechanical foaming material for exterior wall thermal insulation reinforcement according to claim 1, characterized in that: The curing agent is selected from any one of N-aminoethylpiperazine and diethylenetriamine; the surfactant is selected from any one of surfactant AMPHITOL24B and surfactant EMAL TD.

3. The mechanical foaming material for exterior wall thermal insulation reinforcement according to claim 1, characterized in that: The preparation method of the phosphorus-modified nano-silicon dioxide is as follows: (1) Under ice bath conditions, 2-vinylpropane-1,3-diol and triethylamine were added to a dichloromethane solvent, stirred and mixed, and then diphenyl chlorophosphate was added thereto, stirred and reacted for 1-2 hours, and then the temperature was raised to room temperature and the reaction was continued for 6-12 hours. After the reaction was completed, the mixture was washed with deionized water and saturated brine in sequence, dried, and rotary evaporated to obtain intermediate 1; (2) In an ice bath, aminopropyl triethoxysilane and a polymerization inhibitor are added to a toluene solvent, stirred and dispersed, and then the intermediate 1 is added thereto, stirred and reacted for 20-40 minutes, heated to 25-40°C, and continued to react for 5-10 hours. After the reaction is completed, the intermediate 2 is washed with deionized water, rotary evaporated, and dried to obtain the intermediate 2; (3) Under a nitrogen atmosphere, add nano-silica and intermediate 2 into a toluene solvent, raise the temperature to 100-110° C., stir and react for 8-12 hours. After the reaction is completed, filter, wash with toluene, and dry to obtain phosphorus-modified nano-silica.

4. The mechanical foaming material for exterior wall thermal insulation reinforcement according to claim 3, characterized in that: In the above (1), the mass ratio of 2-vinylpropane-1,3-diol, triethylamine and diphenyl chlorophosphate is 1:2-2.5:5-5.

8.

5. The mechanical foaming material for exterior wall thermal insulation reinforcement according to claim 3, characterized in that: In the above (2), the mass ratio of aminopropyltriethoxysilane to intermediate 1 is 1:5-6.

6. The mechanical foaming material for exterior wall thermal insulation reinforcement according to claim 3, characterized in that: In the above (2), the polymerization inhibitor is 4-methoxyphenol, and its usage is 4-8% of the total mass of aminopropyltriethoxysilane and intermediate 1.

7. The mechanical foaming material for exterior wall thermal insulation reinforcement according to claim 3, characterized in that: In the above (3), the mass ratio of nano-silicon dioxide to intermediate 2 is 1:0.25-0.8.

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