CN115196931A - A kind of thermal insulation board for building exterior wall and its manufacturing method - Google Patents

Abstract

The invention discloses a method for manufacturing a thermal insulation board for an exterior wall of a building, comprising the following steps: mixing a three-dimensional ordered macroporous metal-organic frame material and reinforcing fibers and stirring them evenly, then adding an appropriate amount of deionized water to fully dissolve, and then adding Slowly add sodium methanesulfonate solution dropwise, place the solution in an ultrasonic environment to react after the dropwise addition, filter, wash and dry after the reaction to obtain the first product; The first product and the auxiliary materials are mixed and fully stirred to obtain the second product; the second product and the inorganic adhesive slurry are mixed and stirred evenly, and then added into three rollers for extrusion, and after extrusion, a solidified embryo is formed. The solidified embryo body is cured under certain conditions and then demoulded to obtain a semi-finished product; the above-mentioned semi-finished product is put into a fuel-fired hot air furnace to heat up, and is cured, dried and cut to make a finished product. The thermal insulation board of the invention has good fire resistance, high compressive strength and low thermal conductivity.

Description

A kind of thermal insulation board for building exterior wall and its manufacturing method

technical field

The invention belongs to the technical field of thermal insulation boards for buildings, and particularly relates to a thermal insulation board for external walls of buildings and a manufacturing method thereof.

Background technique

With the implementation of building fire protection policies, fire insulation materials have become the mainstream trend, various A-class insulation boards have emerged one after another, and many fireproof modified insulation boards have appeared. However, the excessive pursuit of fireproof performance leads to some shortcomings such as decreased thermal insulation performance, reduced strength, and poor material stability of some A-level insulation boards, resulting in problems such as brittleness, water absorption, and pulverization of insulation boards. caused serious consequences.

Three-dimensional ordered macroporous (3DOM) material refers to a porous structure with a single pore size (pore size greater than 50 nm), and the pore structure is ordered in three-dimensional space. Each hole is connected to the surrounding twelve holes through hole windows. It can be an inorganic material or an organic polymer, and the pore size can be adjusted in the nano-micron range. In addition, the pore surface can be chemically modified to give it new functions. It has a wide range of application prospects as separation materials, catalysts, catalyst carriers, immobilized enzymes and photonic crystals, etc. At the same time, it also provides basic research on the interaction between substances, energy transfer, and the behavior of substances under extreme conditions. Model.

Metal-organic frameworks (MOFs) are a kind of coordination polymers that have developed rapidly in the past decade. They have a three-dimensional pore structure. Generally, metal ions are used as connection points, and organic ligands are supported to form a spatial 3D extension. Another important new class of porous materials other than nanotubes has a wide range of applications in catalysis, energy storage and separation. MOFs have good applications in catalysis, adsorption separation and recognition due to their tunable structures. In recent years, the functionalization of MOFs by post-modification methods can adjust their physical and chemical properties, so that the modified MOFs can be applied in more fields.

Three-dimensional ordered macroporous metal-organic frameworks (3DOM-MOFs) are composites formed by combining three-dimensional ordered macroporous (3DOM) materials and metal-organic frameworks (MOFs). The oriented pore structure has the advantages of both macropores and small pores, and a large specific surface area.

At present, there is no report on the manufacture of thermal insulation boards using three-dimensional ordered macroporous metal-organic framework materials as raw materials.

SUMMARY OF THE INVENTION

The main purpose of the present invention is to overcome the deficiencies in the prior art, and to provide a thermal insulation board for building exterior walls and a manufacturing method thereof. The thermal insulation board of the invention has good fire resistance, high compressive strength and low thermal conductivity.

The purpose of the present invention and the solution to its technical problems are achieved by adopting the following technical solutions.

The invention provides a method for manufacturing a thermal insulation board for an exterior wall of a building, comprising the following steps:

Mix the three-dimensional ordered macroporous metal-organic framework material and the reinforcing fibers in a mass ratio of 1:(0.01~0.1) and stir evenly, then add an appropriate amount of deionized water to fully dissolve, and then slowly drip the concentration of 0.011~0.03 The wt% sodium methanesulfonate solution is stirred while dripping, and after the dripping is completed, the solution is placed in an ultrasonic environment to react, and after the reaction is completed, it is filtered, washed, and dried to obtain the first product;

According to the percentage by weight, 20-30% heavy calcium carbonate, 20-25% coal-to-liquid residue, 40-60% first product and 5-10% auxiliary materials are mixed and fully stirred to obtain the second product;

The second product and the inorganic adhesive slurry are mixed according to the mass ratio of 1:1.5 and stirred evenly, and then added into three rollers for extrusion. Demoulding after curing to obtain semi-finished products;

Put the above semi-finished products into a fuel-fired hot blast stove to heat up, heat up to 40~45℃, and maintain the humidity at 80-90% for 24~30h, take them out and place them in a ventilated place for drying, and keep the moisture content Cut at 15-18% to make the finished product.

Further, the three-dimensional ordered macroporous metal-organic framework material is prepared according to the following method:

a. Take an appropriate amount of PS (polystyrene) emulsion, and then centrifuge at 3000~5000r/h for 6~8h and remove the supernatant to get the bottom precipitate, and then dry the precipitate at 80~100℃ overnight to obtain PS in an orderly arrangement template;

b. Immerse the PS template obtained above in 0.02~0.08g/mL metal salt/methanol solution for 1~3h, then take it out, dry it overnight, and then immerse it again in 0.05~0.15g/mL ligand/methanol solution for static Set for 40~56h to obtain PS/organic framework composite material;

c. Immerse the PS/organic framework composite material in DMF, and remove the PS after stirring for 20-36 h to obtain a three-dimensional ordered macroporous-organic framework material.

Further, in the step a, the metal salt is selected from one of cobalt nitrate, copper nitrate, zinc nitrate, and zirconium nitrate.

Further, in the step b, the ligand is selected from one of 2-methylimidazole, H4adip, and terephthalic acid.

Further, the addition amount of the sodium methanesulfonate solution is carried out according to the amount ratio of the three-dimensional ordered macroporous metal-organic framework material as 0.01ml:1g.

Further, the ultrasonic conditions are: frequency 80~100KHz, time 30~40min.

Further, the auxiliary material is polystyrene.

Further, the inorganic viscose slurry is prepared according to the following method: the ordinary Portland cement and the fast-hardening sulfoaluminate cement are put into the reaction vessel in a mass ratio of 1:3 to 5 and are fully stirred to obtain. .

Further, the pressure of the extrusion is 2-3 kg/cm ² .

With the above technical solutions, the present invention has at least the following advantages: the three-dimensional ordered macroporous metal-organic framework material (3DOM-MOFs) of the present invention is a kind of material with a regular and ordered pore structure, and has both macropores and micropores. This kind of pore structure has the functions of sound insulation and heat insulation. In the present invention, three-dimensional ordered macroporous metal-organic framework materials (3DOM-MOFs) are mixed with reinforcing fibers, and then through the action of sodium methanesulfonate, the reinforcing fibers are adsorbed on the pores of the three-dimensional ordered macroporous metal-organic framework materials. Thus, the toughness and compressive strength of three-dimensional ordered macroporous metal-organic frameworks are improved. After testing, the fireproof performance of the thermal insulation board of the present invention reaches A grade, the thermal conductivity can reach 0.032 when the bulk density is 140~160kg/m³, and the tensile strength and compressive strength are obviously improved.

The above description is only an overview of the technical solution of the present invention. In order to understand the technical means of the present invention more clearly, and to implement according to the content of the description, the preferred embodiments of the present invention are described in detail below.

Detailed ways

In order to make it easy to understand the technical means, creative features, goals and effects realized by the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments It is only a part of the embodiments of the present invention, but not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

Example 1

Preparation of three-dimensional ordered macroporous metal-organic framework materials: take an appropriate amount of PS (polystyrene) emulsion and centrifuge at 4000 r/h for 6 h, and then remove the supernatant to obtain the bottom precipitate. Ordered PS templates were obtained after drying at 90°C overnight. It was immersed in 0.05 g/mL cobalt nitrate/methanol solution for 2 hours, and then the PS template was taken out and dried overnight. The PS template immersed in cobalt nitrate/methanol solution was immersed in 0.1 g/mL 2-methylimidazole/methanol solution and allowed to stand for 48 hours to prepare PS/organic framework composites. The PS/organic framework composites were immersed in DMF, and the PS was removed after stirring for 24 h to obtain 3D ordered macroporous-organic frameworks.

The three-dimensional ordered macroporous metal-organic framework material and the reinforcing fibers were mixed and stirred uniformly in a mass ratio of 1:0.05, and then an appropriate amount of deionized water was added to fully dissolve, and then 0.02wt% methyl sulfonic acid was slowly added dropwise. Sodium solution (the ratio of the three-dimensional ordered macroporous metal-organic framework material is 0.01ml:1g), stir while adding dropwise, put the solution at 90 KHz for ultrasonic reaction for 35min after the dropwise addition, wait for the reaction After completion, filter, wash and dry to obtain the first product.

According to the percentage by weight, 25% heavy calcium carbonate, 20% coal-to-liquid residue, 50% first product and 5% polystyrene are mixed and fully stirred to obtain the second product;

The second product and the inorganic adhesive slurry (the ordinary Portland cement and the fast-hardening sulfoaluminate cement are put into the reaction vessel according to the mass ratio of 1:4 and are fully stirred and obtained) are 1:1 according to the mass ratio: The amount of 1.5 is mixed and stirred evenly, and then added into three rollers for extrusion, and the extrusion pressure is set to 2 kg/cm ² . Demoulding, a semi-finished product is obtained.

Put the above semi-finished products into a fuel-fired hot blast stove to heat up, heat up to 42°C, and maintain the humidity at 80-90% for 27 hours. After taking them out, place them in a ventilated place for drying, and keep their moisture content at 15-18 % is cut to make the finished product.

Example 2

Preparation of three-dimensional ordered macroporous metal-organic framework materials: take an appropriate amount of PS (polystyrene) emulsion and centrifuge at 5000 r/h for 8 h, and then remove the supernatant to obtain the bottom precipitate. Ordered PS templates were obtained after drying at 90°C overnight. It was immersed in 0.08 g/mL cobalt nitrate/methanol solution for 2 hours, and then the PS template was taken out and dried overnight. The PS template immersed in zinc nitrate/methanol solution was immersed in 0.05 g/mL terephthalic acid/methanol solution, and left for 48 hours to prepare PS/organic framework composites. The PS/organic framework composites were immersed in DMF, and the PS was removed after stirring for 24 h to obtain 3D ordered macroporous-organic frameworks.

The three-dimensional ordered macroporous metal-organic framework material and the reinforcing fibers were mixed and stirred uniformly in a mass ratio of 1:0.01, and then an appropriate amount of deionized water was added to fully dissolve, and then slowly dripped with a concentration of 0.03wt% methanesulfonic acid Sodium solution (the ratio of the three-dimensional ordered macroporous metal-organic framework material is 0.01ml:1g), stir while adding dropwise, put the solution under 100 KHz ultrasonic reaction for 30min after the dropwise addition, wait for the reaction After completion, filter, wash and dry to obtain the first product.

According to the percentage by weight, 30% heavy calcium carbonate, 20% coal-to-liquid residue, 40% first product and 10% polystyrene are mixed and fully stirred to obtain the second product;

The second product and the inorganic adhesive slurry (the ordinary Portland cement and the fast-hardening sulfoaluminate cement are put into the reaction vessel according to the mass ratio of 1:5 and are fully stirred to obtain) are 1 according to the mass ratio: The amount of 1.5 is mixed and stirred evenly, and then added into three rollers for extrusion, and the extrusion pressure is set to 2 kg/cm ² . Demoulding, a semi-finished product is obtained.

Put the above semi-finished products into a fuel-fired hot blast stove to heat up, heat up to 45°C, and maintain the humidity at 80-90% for 24 hours. After taking them out, place them in a ventilated place for drying, and keep their moisture content at 15-18 % is cut to make the finished product.

Example 3

Preparation of three-dimensional ordered macroporous metal-organic framework materials: take an appropriate amount of PS (polystyrene) emulsion and centrifuge at 4000 r/h for 6 h, and then remove the supernatant to obtain the bottom precipitate. Ordered PS templates were obtained after drying at 90°C overnight. It was immersed in 0.08 g/mL cobalt nitrate/methanol solution for 2 hours, and then the PS template was taken out and dried overnight. The PS template immersed in copper nitrate/methanol solution was immersed in 0.05 g/mL H4adip/methanol solution and left to stand for 48 hours to prepare PS/organic framework composites. The PS/organic framework composites were immersed in DMF, and the PS was removed after stirring for 24 h to obtain 3D ordered macroporous-organic frameworks.

The three-dimensional ordered macroporous metal-organic framework material and the reinforcing fibers were mixed and stirred uniformly in a mass ratio of 1:0.1, then an appropriate amount of deionized water was added to fully dissolve, and then 0.01wt% methyl sulfonic acid was slowly added dropwise. Sodium solution (the ratio of the three-dimensional ordered macroporous metal-organic framework material is 0.01ml: 1g), stir while adding dropwise, put the solution into ultrasonic reaction at 80 KHz for 40min after the dropwise addition, wait for the reaction After completion, filter, wash and dry to obtain the first product.

According to the percentage by weight, 20% of heavy calcium carbonate, 25% of coal-to-liquid residue, 50% of the first product and 5% of polystyrene are mixed and fully stirred to obtain the second product;

The second product and the inorganic adhesive slurry (the ordinary Portland cement and the fast-hardening sulfoaluminate cement are put into the reaction vessel according to the mass ratio of 1:3 and are fully stirred and obtained) are 1:3 according to the mass ratio: The amount of 1.5 is mixed and stirred evenly, and then added into three rollers for extrusion, and the extrusion pressure is set to 3 kg/cm ² . Demoulding, a semi-finished product is obtained.

Put the above semi-finished products into a fuel-fired hot blast stove to heat up, heat up to 40°C, and maintain the humidity at 80-90% for 30 hours. After taking them out, place them in a ventilated place for drying, and keep their moisture content at 15-18 % is cut to make the finished product.

Comparative Example 1

According to the percentage by weight, 25% heavy calcium carbonate, 20% coal-to-oil residue, 50% reinforcing fiber and 5% polystyrene are mixed and fully stirred to obtain a product;

The above product and inorganic adhesive slurry (common portland cement and fast-hardening sulfoaluminate cement are put into the reaction vessel according to the mass ratio of 1:4 and fully stirred to obtain) according to the mass ratio of 1:1.5 Mix and stir evenly, then add it into three rollers for extrusion, set the extrusion pressure to 2 kg/cm2, and form a solidified embryo after extrusion. The solidified embryo is demolded after curing under certain conditions. , a semi-finished product is obtained.

Put the above semi-finished products into a fuel-fired hot blast stove to heat up, heat up to 42°C, and maintain the humidity at 80-90% for 27 hours. After taking them out, place them in a ventilated place for drying, and keep their moisture content at 15-18 % is cut to make the finished product.

Test Example 1 Performance Evaluation of Thermal Insulation Board

The thermal insulation boards obtained in Examples 1 to 3 and Comparative Example 1 were subjected to performance measurements such as compressive strength and thermal conductivity. The performance evaluation of the thermal insulation boards was based on CECS standards, and the measurement results were shown in Table 1 below.

Table 1 Summary of performance of insulation board

From the results in Table 1, it can be seen that the fire resistance of the silica rock thermal insulation board modified by graphene material reaches Grade A, and the thermal conductivity can reach 0.032 when the bulk density is 140~160kg/m³, and the performance in all aspects is significantly higher than that of the comparative implementation. example 1. After the thermal insulation board of the present invention is manufactured, it can be reinforced and compounded with a 1mm-thick composite glass fiber mesh cloth on both sides, which further improves the stability of the thermal insulation board and enhances the harmony between the thermal insulation board and the bonding mortar and plastering mortar. Anisotropy and cohesion.

The above are only preferred embodiments of the present invention, and do not limit the present invention in any form. Although the present invention has been disclosed above with preferred embodiments, it is not intended to limit the present invention. The technical personnel, within the scope of the technical solution of the present invention, can make some changes or modifications to equivalent examples of equivalent changes by using the methods and technical contents disclosed above, provided that the content of the technical solution of the present invention is not departed from, Any simple modifications, equivalent changes and modifications made to the above embodiments according to the technical essence of the present invention still fall within the scope of the technical solutions of the present invention.

Claims (10)

1. a manufacture method of thermal insulation board for building exterior wall, is characterized in that, comprises the following steps: The three-dimensional ordered macroporous metal-organic framework material and the reinforcing fiber are mixed in a mass ratio of 1: (0.01~0.1) and stirred evenly, then add an appropriate amount of deionized water to fully dissolve, and then slowly dropwise add the concentration of 0.01~0.03 The wt% sodium methanesulfonate solution is stirred while dripping, and after the dripping is completed, the solution is placed in an ultrasonic environment to react, and after the reaction is completed, it is filtered, washed, and dried to obtain the first product; According to the percentage by weight, 20-30% heavy calcium carbonate, 20-25% coal-to-liquid residue, 40-60% first product and 5-10% auxiliary materials are mixed and fully stirred to obtain the second product; The second product and the inorganic adhesive slurry are mixed according to the mass ratio of 1:1.5 and stirred evenly, and then added into three rollers for extrusion. Demoulding after curing to obtain semi-finished products; Put the above semi-finished products into a fuel-fired hot blast stove to heat up, heat up to 40~45℃, and maintain the humidity at 80-90% for 24~30h, take them out and place them in a ventilated place for drying, and keep the moisture content Cut at 15-18% to make the finished product. 2. The manufacturing method of a thermal insulation board for building exterior walls according to claim 1, wherein the three-dimensional ordered macroporous metal-organic frame material is prepared according to the following method: a. Take an appropriate amount of PS (polystyrene) emulsion, and then centrifuge at 3000~5000r/h for 6~8h and remove the supernatant to get the bottom precipitate, and then dry the precipitate at 80~100℃ overnight to obtain PS in an orderly arrangement template; b. Immerse the PS template obtained above in 0.02~0.08g/mL metal salt/methanol solution for 1~3h, then take it out, dry it overnight, and then immerse it again in 0.05~0.15g/mL ligand/methanol solution for static Set for 40~56h to obtain PS/organic framework composite material; c. Immerse the PS/organic framework composite material in DMF, and remove the PS after stirring for 20-36 h to obtain a three-dimensional ordered macroporous-organic framework material. 3. the manufacture method of a kind of thermal insulation board for building exterior wall according to claim 2, is characterized in that, described in the step a, the metal salt is selected from cobalt nitrate, copper nitrate, zinc nitrate, zirconium nitrate. A sort of. 4. the manufacture method of a kind of thermal insulation board for building exterior wall according to claim 2, is characterized in that, described part in described step b is selected from in 2-methylimidazole, H4adip, terephthalic acid a kind of. 5. the manufacture method of a kind of thermal insulation board for building exterior wall according to claim 1, is characterized in that, the add-on of described sodium methanesulfonate solution is according to the three-dimensional ordered macroporous metal-organic framework material according to the add-on The amount ratio was 0.01ml:1g. 6 . The method for manufacturing a thermal insulation board for building exterior walls according to claim 1 , wherein the ultrasonic conditions are: frequency 80-100KHz, time 30-40min. 7 . 7 . The method for manufacturing a thermal insulation board for building exterior walls according to claim 1 , wherein the auxiliary material is polystyrene. 8 . 8. The manufacturing method of a thermal insulation board for building exterior walls according to claim 1, wherein the inorganic viscose slurry is prepared according to the following method: ordinary Portland cement and fast-hardening aluminum The acid salt cement is put into a reaction vessel in a mass ratio of 1:3 to 5 and fully stirred to obtain it. 9 . The method for manufacturing a thermal insulation board for an exterior wall of a building according to claim 1 , wherein the extrusion pressure is 2-3 kg/cm ² . 10 . 10 . The method for manufacturing a thermal insulation board for building exterior walls according to claim 1 , wherein the curing conditions for the solidified embryo body are as follows: a temperature of 30-32° C. and a time of 1-4 hours. 11 .