CN111909484A - In-situ nano modified phenolic resin building thermal insulation material and preparation method thereof - Google Patents

In-situ nano modified phenolic resin building thermal insulation material and preparation method thereof Download PDF

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CN111909484A
CN111909484A CN202010982580.4A CN202010982580A CN111909484A CN 111909484 A CN111909484 A CN 111909484A CN 202010982580 A CN202010982580 A CN 202010982580A CN 111909484 A CN111909484 A CN 111909484A
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phenolic resin
thermal insulation
insulation material
modified phenolic
building thermal
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CN111909484B (en
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李军心
李建辉
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China Construction Fourth Engineering Division Corp Ltd
China Construction Fourth Engineering Bureau Construction and Development Co Ltd
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China Construction Fourth Engineering Division Corp Ltd
China Construction Fourth Engineering Bureau Construction and Development Co Ltd
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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    • C08J9/0071—Nanosized fillers, i.e. having at least one dimension below 100 nanometers
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    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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    • C08J2361/10—Phenol-formaldehyde condensates
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Abstract

The invention provides a preparation method of an in-situ nano modified phenolic resin building thermal insulation material, which comprises the following steps: s1, high-temperature roasting the cyanamide compound in the oxygen-deficient atmosphere to obtain C3N4A material; s2, mixing C3N4Pretreating the material in acid to obtain protonized C3N4A colloidal solution; s3, adding protonized C3N4Use of colloidal solutions for curing phenolic resole resin systemsAnd (4) carrying out chemical reaction to obtain the in-situ nano modified phenolic resin building thermal insulation material. The material has high strength and excellent flame retardant property.

Description

In-situ nano modified phenolic resin building thermal insulation material and preparation method thereof
Technical Field
The invention relates to an in-situ nano modified phenolic resin building thermal insulation material and a preparation method thereof, belonging to the technical field of building materials.
Background
The phenolic resin is prepared by the polycondensation reaction of phenolic compounds and aldehyde compounds under the action of acidic or basic catalysts. Phenol resins are widely used in building materials because of their excellent heat resistance, processability, flame retardancy, and low smoke generation during combustion. However, the molecules of the phenolic resin are mostly in a three-dimensional structure, and are rich in rigid benzene rings linked by methylene, so that the brittleness of the matrix is high, stress is easily generated on the surface, and the construction is not facilitated, so that a toughening agent such as ethylene glycol, polyethylene glycol and the like is generally required to be added. However, these toughening agents are often flammable, and reduce the fire resistance of the phenolic resin, so that a flame retardant needs to be added to further improve the fire resistance of the phenolic resin. At present, the commonly used phenolic resin flame retardant is cyanamide compounds such as melamine and the like. However, melamine and other cyanamide compounds tend to have large particles and are difficult to uniformly disperse, so that the flame retardant effect is not ideal.
Disclosure of Invention
The invention provides an in-situ nano modified phenolic resin building thermal insulation material and a preparation method thereof, which can effectively solve the problems.
The invention is realized by the following steps:
a preparation method of an in-situ nano modified phenolic resin building thermal insulation material comprises the following steps:
s1, high-temperature roasting the cyanamide compound in the oxygen-deficient atmosphere to obtain C3N4A material;
s2, mixing C3N4Pretreating the material in acid to obtain protonized C3N4A colloidal solution;
s3, adding protonized C3N4The colloidal solution is used for curing an A-stage phenolic resin system to obtain the in-situ nano modified phenolic resin building thermal insulation material.
As a further improvement, the cyanamide compound is one or more selected from dicyandiamide, melamine and urea.
As a further improvement, the high-temperature roasting is carried out at the temperature of 500-650 ℃ for 2-4 hours, and then the temperature is naturally reduced.
As a further improvement, the acid is selected from one or more of sulfuric acid, phosphoric acid, phenolsulfonic acid and p-toluenesulfonic acid.
As a further modification, in step S2, C is3N4The mass percentage of the material in the whole reaction system is 5-20%.
As a further improvement, the pretreatment is to mix C3N4The material is placed in the acid and stirred for 0.2-1 hour to obtain a transparent colloid acidic solution.
As a further improvement, step S3 further includes the steps of:
s31, mixing phenol and paraformaldehyde, adding an alkaline catalyst, carrying out a polymerization reaction, and adding urea after the reaction is finished to obtain A-stage phenolic resin;
s32, converting the A-stage phenolic resin into protonized C3N4And (3) blending the colloidal solution, the foaming agent, the foam stabilizer and the reinforcing agent, and heating, foaming and curing to obtain the in-situ nano modified phenolic resin building thermal insulation material.
As a further improvement, the mass parts of the components in the step S32 are: 80-100 parts of A-stage phenolic resin and protonated C3N45-20 parts of colloidal solution, 0.5-10 parts of curing agent, 0.5-5 parts of foaming agent, 0.1-3 parts of foam stabilizer and 1-20 parts of reinforcing agent.
As a further improvement, the curing temperature is 50-120 ℃ and the curing time is 5-20 min.
An in-situ nano modified phenolic resin building thermal insulation material prepared by the method.
The invention has the beneficial effects that:
the invention abandons the idea of directly introducing cyanamide compounds such as melamine and the like into the phenolic resin building heat-insulating material, and adopts the product C after the high-temperature decomposition of the cyanamide compounds3N4By using C3N4Easily protonate in phenolic resin curing agent such as sulfuric acid or phosphoric acid to obtain nanoscale C3N4Colloidal solution of C3N4The clear colloidal acidic solution of fragments is used for curing of the phenolic resole resin system. The method belongs to the field of in-situ polymerization, but does not need to be performed reverselyThe reaction product is subjected to complex modification to improve the compatibility among the components.
The invention utilizes C3N4Readily protonatable in sulfuric or phosphoric acid to give C3N4The colloidal acidic solution, and sulfuric or phosphoric acid is just a catalyst for the curing of the phenolic resole resin. When these acids are mixed homogeneously with the phenolic resin, C may be added3N4The nano-segments are rapidly and uniformly dispersed in the framework of the phenolic resin, and the C3N4The nano segments are similar to stones in concrete, the three-dimensional rigid chains of the phenolic resin are similar to steel bars, and the nano segments and the three-dimensional rigid chains can form a three-dimensional space structure similar to the form of the steel bars, so that the strength of the building heat-insulating material can be obviously improved, and the tensile modulus of the building heat-insulating material is obviously improved.
The invention utilizes the method of in-situ polymerization and solidification to mix C3N4Nano-fragments dispersed rapidly and uniformly in the skeleton of phenolic resin, C3N4The nanometer fragments and phosphoric acid or sulfuric acid reach molecular level dispersion and interaction, and the synergistic flame retardant effect of a large number of short-range P-N or S-N bonds is formed, so that the flame retardant capability of the building heat-insulating material is greatly improved, and the oxygen index of the building heat-insulating material is compared with that of the building heat-insulating material without doped C3N4The material of (2) is greatly improved.
In situ polymerization C employed in the present invention3N4The process of the nano-segment has the characteristics of simple operation, low cost, simple and convenient process and high production efficiency, and can simultaneously improve the flame retardance and the strength of the phenolic resin building thermal insulation material to obtain the high-quality phenolic resin building thermal insulation material.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention are described clearly and completely below, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. Thus, the following detailed description of embodiments of the invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
In the description of the present invention, the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
A preparation method of an in-situ nano modified phenolic resin building thermal insulation material comprises the following steps:
s1, high-temperature roasting the cyanamide compound in the oxygen-deficient atmosphere to obtain C3N4A material; the oxygen-deficient atmosphere refers to that the cyanamide compound is placed in a covered crucible or coated in an aluminum foil with micropores on the surface, and the roasting atmosphere can be inert atmosphere or air; the cyanamide compound can be decomposed into C by high-temperature roasting3N4A material.
S2, mixing C3N4Pretreatment of the material in acid, C3N4Protonation of the material in acid to give protonated C3N4A colloidal solution.
S3, adding protonized C3N4The colloidal solution is used for curing an A-stage phenolic resin system to obtain the in-situ nano modified phenolic resin building thermal insulation material. This operation in situ will be3N4The nano-scale high-dispersion material is highly dispersed in a phenolic resin foam body and forms a structure similar to a reinforced concrete type with a phenolic resin three-dimensional structure, so that the strength of the phenolic resin building thermal insulation material is obviously improved.
As a further improvement, the cyanamide compound is one or more selected from dicyandiamide, melamine and urea.
As a further improvement, the high-temperature roasting is carried out at the temperature of 500-650 ℃ for 2-4 hours, and then the temperature is naturally reduced. If the temperature is lower than 500 ℃, qualified C cannot be obtained3N4If the temperature is higher than 650 ℃ then C3N4The yield was too low.
As a further improvement, the acid is selected from one or more of sulfuric acid, phosphoric acid, phenolsulfonic acid and p-toluenesulfonic acid. C3N4A large number of short-range P-N or S-N bonds formed by the molecular-level dispersion and interaction of the fragments and sulfuric acid, phosphophenolsulfonic acid or P-toluenesulfonic acid can play a synergistic flame-retardant role, so that the flame-retardant capability of the phenolic resin building thermal insulation material is greatly improved.
As a further modification, in step S2, C is3N4The mass percentage of the material in the whole reaction system is 5-20%, if the mass percentage is lower than 5%, the flame retardant property cannot be obviously improved, and if the mass percentage is higher than 20%, the tensile strength is too low.
As a further improvement, the pretreatment is to mix C3N4The material is placed in the acid and stirred for 0.2-1 hour to obtain a transparent colloid acidic solution.
As a further improvement, step S3 further includes the steps of:
s31, mixing phenol and paraformaldehyde, adding an alkaline catalyst, carrying out a polymerization reaction, and adding urea after the reaction is finished to obtain A-stage phenolic resin;
s32, converting the A-stage phenolic resin into protonized C3N4And (3) blending the colloidal solution, the foaming agent, the foam stabilizer and the reinforcing agent, and heating, foaming and curing to obtain the in-situ nano modified phenolic resin building thermal insulation material.
As a further improvement, the alkaline catalyst is sodium hydroxide or magnesium hydroxide aqueous solution with the mass concentration of 15-25%; the mass concentration is preferably 20%.
As a further improvement, the mass parts of the components in the step S31 are: 80-100 parts of phenol, 30-50 parts of paraformaldehyde, 10-30 parts of an alkaline catalyst and 1-10 parts of urea.
As a further improvement, the temperature of the polymerization reaction is 70-90 ℃, and the polymerization time is 1-4 hours.
As a further improvement, the mass parts of the components in the step S32 are: 80-100 parts of A-stage phenolic resin and protonated C3N45-20 parts of colloidal solution, 0.5-10 parts of curing agent, 0.5-5 parts of foaming agent, 0.1-3 parts of foam stabilizer and 1-20 parts of reinforcing agent. The proportion of the foaming agent and the foam stabilizer is moderate, otherwise, the obtained thermal insulation material cannot foam or foam is excessively foamed to cause foam collapse. The addition of the reinforcing agent cannot be too high, otherwise, the tensile strength of the obtained heat-insulating material is reduced, the apparent density is increased, and the heat conductivity coefficient is increased.
As a further improvement, the foaming agent is one or more of n-pentane and n-hexane; the foam stabilizer is one or more of tween-80, an organic silicon foam stabilizer and simethicone; the reinforcing agent is one or more of aluminum hydroxide, magnesium hydroxide, white carbon black and zinc borate.
As a further improvement, the curing temperature is 50-120 ℃ and the curing time is 5-20 min. The curing temperature is too low or too high, and the curing time is too long or too short, so that the foam body is not foamed or is excessively foamed to collapse.
An in-situ nano modified phenolic resin building thermal insulation material prepared by the method.
The following is a description by way of specific examples.
Example 1
Weighing a certain amount of melamine, coating the melamine in an aluminum foil with micropores on the surface, placing the aluminum foil in a muffle furnace, roasting the melamine for 3 hours at 600 ℃, and naturally cooling to obtain C3N4And (5) producing the product.
100g of 2mol/L sulfuric acid are weighed out and 25g of C are added3N4The product is stirred for 0.5 hour to obtain a transparent colloid sulfuric acid solution.
100g of phenol, 40g of paraformaldehyde, 15g of 20% Mg (OH) are weighed out2Heating the aqueous solution to 65 ℃ at the speed of 2 ℃/min, reacting for half an hour, heating to 85 ℃ at the same speed,and naturally cooling to 65 ℃ after reacting for 1 hour, then adding 4 parts of urea, stopping the reaction after reacting for half an hour, and naturally cooling to obtain the A-stage phenolic resin.
Weighing 100g of A-stage phenolic resin, 3g of n-pentane, 1g of tween-80 and 8g of aluminum hydroxide, uniformly stirring, and adding 8g of the protonized C-containing material3N4And stirring the colloidal sulfuric acid solution uniformly again, placing the mixture into a mold, placing the mold into a drying oven at 100 ℃ for heating for 10min, taking out the mold, cooling and demolding to obtain the in-situ nano modified phenolic resin building thermal insulation material.
The apparent density of the sample was 50kg/m as measured by gravimetric-volumetric measurement3The heat conductivity coefficient measured by a heat conductivity coefficient instrument is 0.023W/mK, the oxygen index measured by an oxygen index instrument is 43, the tensile strength measured by a mechanical universal tester is 0.10MPa, and the sample reaches B1-grade flame retardant.
Example 2
Weighing a certain amount of melamine, coating the melamine in an aluminum foil with micropores on the surface, placing the aluminum foil in a muffle furnace, roasting the melamine for 3 hours at 600 ℃, and naturally cooling to obtain C3N4And (5) producing the product.
100g of 2mol/L sulfuric acid are weighed out and 25g of C are added3N4The product is stirred for 0.5 hour to obtain a transparent colloid sulfuric acid solution.
100g of phenol, 40g of paraformaldehyde, 15g of 20% Mg (OH) are weighed out2Heating the aqueous solution to 65 ℃ at the speed of 2 ℃/min, reacting for half an hour, heating to 85 ℃ at the same speed, naturally cooling to 65 ℃ after reacting for 1 hour, then adding 4 parts of urea, stopping the reaction after reacting for half an hour, and naturally cooling to obtain the A-stage phenolic resin.
Weighing 100g of A-stage phenolic resin, 3g of n-pentane, 1g of tween-80 and 8g of aluminum hydroxide, uniformly stirring, and adding 8g of the protonized C-containing material3N4And stirring the colloidal sulfuric acid solution uniformly again, placing the mixture into a mold, placing the mold into a drying oven at 100 ℃ for heating for 10min, taking out the mold, cooling and demolding to obtain the in-situ nano modified phenolic resin building thermal insulation material.
The procedure of example 1 was otherwise the same as that of example 1, except that phosphoric acid was used in place of sulfuric acid.
The apparent density of the sample was tested to be 51kg/m3The heat conductivity coefficient is 0.023W/mK, the oxygen index is 42, the tensile strength is 0.10MPa, and the sample reaches B1 flame retardant grade.
Example 3
Weighing a certain amount of dicyandiamide, coating the dicyandiamide in an aluminum foil with micropores on the surface, placing the aluminum foil in a muffle furnace, roasting the aluminum foil for 3 hours at 500 ℃, and naturally cooling to obtain C3N4And (5) producing the product.
100g of 2mol/L sulfuric acid are weighed out and 20g of C are added3N4The product is stirred for 0.5 hour to obtain a transparent colloid sulfuric acid solution.
100g of phenol, 40g of paraformaldehyde, 15g of 20% Mg (OH) are weighed out2Heating the aqueous solution to 65 ℃ at the speed of 2 ℃/min, reacting for half an hour, heating to 85 ℃ at the same speed, naturally cooling to 65 ℃ after reacting for 1 hour, then adding 4 parts of urea, stopping the reaction after reacting for half an hour, and naturally cooling to obtain the A-stage phenolic resin.
Weighing 100g of A-stage phenolic resin, 3g of n-pentane, 1g of tween-80 and 8g of aluminum hydroxide, uniformly stirring, and adding 15g of the protonized C-containing material3N4And stirring the colloidal sulfuric acid solution uniformly again, placing the mixture into a mold, placing the mold into a drying oven at 100 ℃ for heating for 10min, taking out the mold, cooling and demolding to obtain the in-situ nano modified phenolic resin building thermal insulation material.
The apparent density of the sample was found to be 54kg/m3The thermal conductivity coefficient is 0.028W/mK, the oxygen index is 38, the tensile strength is 0.12MPa, and the sample reaches the flame-retardant B1 grade.
Example 4
Weighing a certain amount of urea, coating the urea in an aluminum foil with micropores on the surface, placing the aluminum foil in a muffle furnace, roasting the urea for 3 hours at 500 ℃, and naturally cooling to obtain C3N4And (5) producing the product.
100g of 2mol/L sulfuric acid are weighed out and 15g of C are added3N4The product is stirred for 0.5 hour to obtain a transparent colloid sulfuric acid solution.
100g of phenol, 40g of paraformaldehyde, 15g of 20% Mg (OH) are weighed out2Heating the aqueous solution to 65 ℃ at the speed of 2 ℃/min, and reactingAnd (3) raising the temperature to 85 ℃ at the same speed for half an hour, naturally cooling to 65 ℃ after reacting for 1 hour, then adding 4 parts of urea, stopping the reaction after reacting for half an hour, and naturally cooling to obtain the A-stage phenolic resin.
Weighing 100g of A-stage phenolic resin, 3g of n-pentane, 1g of tween-80 and 8g of aluminum hydroxide, uniformly stirring, and adding 15g of the protonized C-containing material3N4And stirring the colloidal sulfuric acid solution uniformly again, placing the mixture into a mold, placing the mold into a drying oven at 100 ℃ for heating for 10min, taking out the mold, cooling and demolding to obtain the in-situ nano modified phenolic resin building thermal insulation material. .
The apparent density of the sample was found to be 56kg/m3The thermal conductivity coefficient is 0.031W/mK, the oxygen index is 40, the tensile strength is 0.12MPa, and the sample reaches the flame retardant B1 grade.
Example 5
Weighing a certain amount of melamine, coating the melamine in an aluminum foil with micropores on the surface, placing the aluminum foil in a muffle furnace, roasting the melamine for 3 hours at 600 ℃, and naturally cooling to obtain C3N4And (5) producing the product.
100g of 2mol/L phenolsulfonic acid are weighed out and 25g of C are added3N4The product is stirred for 0.5 hour to obtain a transparent colloid sulfuric acid solution.
100g of phenol, 40g of paraformaldehyde, 15g of 20% Mg (OH) are weighed out2Heating the aqueous solution to 65 ℃ at the speed of 2 ℃/min, reacting for half an hour, heating to 85 ℃ at the same speed, naturally cooling to 65 ℃ after reacting for 1 hour, then adding 4 parts of urea, stopping the reaction after reacting for half an hour, and naturally cooling to obtain the A-stage phenolic resin.
Weighing 100g of A-stage phenolic resin, 3g of n-pentane, 1g of tween-80 and 8g of aluminum hydroxide, uniformly stirring, and adding 8g of the protonized C-containing material3N4And stirring the colloidal sulfuric acid solution uniformly again, placing the mixture into a mold, placing the mold into a drying oven at 100 ℃ for heating for 10min, taking out the mold, cooling and demolding to obtain the in-situ nano modified phenolic resin building thermal insulation material. .
The apparent density of the sample was measured to be 50kg/m3The heat conductivity coefficient is 0.023W/mK, the oxygen index is 44, the tensile strength is 0.10MPa, and the sample reachesFlame retardant grade B1.
Example 6
Weighing a certain amount of melamine, coating the melamine in an aluminum foil with micropores on the surface, placing the aluminum foil in a muffle furnace, roasting the melamine for 3 hours at 600 ℃, and naturally cooling to obtain C3N4And (5) producing the product.
100g of 2mol/L p-toluenesulfonic acid are weighed out and 25g of C are added3N4The product is stirred for 0.5 hour to obtain a transparent colloid sulfuric acid solution.
100g of phenol, 40g of paraformaldehyde, 15g of 20% Mg (OH) are weighed out2Heating the aqueous solution to 65 ℃ at the speed of 2 ℃/min, reacting for half an hour, heating to 85 ℃ at the same speed, naturally cooling to 65 ℃ after reacting for 1 hour, then adding 4 parts of urea, stopping the reaction after reacting for half an hour, and naturally cooling to obtain the A-stage phenolic resin.
Weighing 100g of A-stage phenolic resin, 3g of n-pentane, 1g of tween-80 and 8g of aluminum hydroxide, uniformly stirring, and adding 8g of the protonized C-containing material3N4And stirring the colloidal sulfuric acid solution uniformly again, placing the mixture into a mold, placing the mold into a drying oven at 100 ℃ for heating for 10min, taking out the mold, cooling and demolding to obtain the in-situ nano modified phenolic resin building thermal insulation material.
The apparent density of the sample was tested to be 51kg/m3The thermal conductivity coefficient is 0.022W/mK, the oxygen index is 41, the tensile strength is 0.10MPa, and the sample reaches the flame-retardant B1 grade.
Example 7
Weighing a certain amount of melamine, coating the melamine in an aluminum foil with micropores on the surface, placing the aluminum foil in a muffle furnace, roasting the melamine for 3 hours at 600 ℃, and naturally cooling to obtain C3N4And (5) producing the product.
100g of 2mol/L sulfuric acid are weighed out and 25g of C are added3N4The product is stirred for 0.5 hour to obtain a transparent colloid sulfuric acid solution.
100g of phenol, 40g of paraformaldehyde, 15g of 20% Mg (OH) are weighed out2Heating the aqueous solution to 65 ℃ at a speed of 2 ℃/min, reacting for half an hour, heating the aqueous solution to 85 ℃ at the same speed, naturally cooling the aqueous solution to 65 ℃ after reacting for 1 hour, adding 4 parts of urea, and reacting for half an hourAnd stopping the reaction, and naturally cooling to obtain the A-stage phenolic resin.
Weighing 100g of A-stage phenolic resin, 2g of n-pentane, 2g of tween-80 and 12g of magnesium hydroxide, uniformly stirring, and adding 15g of the protonized C-containing material3N4And stirring the colloidal sulfuric acid solution uniformly again, placing the mixture into a mold, placing the mold into a drying oven at 100 ℃ for heating for 10min, taking out the mold, cooling and demolding to obtain the in-situ nano modified phenolic resin building thermal insulation material.
The apparent density of the sample was tested to be 42kg/m3The thermal conductivity coefficient is 0.03W/mK, the oxygen index is 36, the tensile strength is 0.14MPa, and the sample reaches the flame-retardant B1 grade.
Example 8
Weighing a certain amount of melamine, coating the melamine in an aluminum foil with micropores on the surface, placing the aluminum foil in a muffle furnace, roasting the melamine for 3 hours at 600 ℃, and naturally cooling to obtain C3N4And (5) producing the product.
100g of 2mol/L sulfuric acid are weighed out and 25g of C are added3N4The product is stirred for 0.5 hour to obtain a transparent colloid sulfuric acid solution.
100g of phenol, 40g of paraformaldehyde, 15g of 20% Mg (OH) are weighed out2Heating the aqueous solution to 65 ℃ at the speed of 2 ℃/min, reacting for half an hour, heating to 85 ℃ at the same speed, naturally cooling to 65 ℃ after reacting for 1 hour, then adding 4 parts of urea, stopping the reaction after reacting for half an hour, and naturally cooling to obtain the A-stage phenolic resin.
Weighing 100g of A-stage phenolic resin, 5g of n-pentane, 2g of tween-80 and 12g of magnesium hydroxide, uniformly stirring, and adding 5g of the protonized C-containing material3N4And stirring the colloidal sulfuric acid solution uniformly again, placing the mixture into a mold, placing the mold into a drying oven at 100 ℃ for heating for 10min, taking out the mold, cooling and demolding to obtain the in-situ nano modified phenolic resin building thermal insulation material.
The apparent density of the sample was tested to be 58kg/m3The thermal conductivity coefficient is 0.021W/mK, the oxygen index is 33, the tensile strength is 0.09MPa, and the sample reaches the flame-retardant B1 grade.
Comparative example 1
100g of phenol and 40g of poly (ethylene glycol)Formaldehyde, 15g of 20% Mg (OH)2Heating the aqueous solution to 65 ℃ at the speed of 2 ℃/min, reacting for half an hour, heating to 85 ℃ at the same speed, naturally cooling to 65 ℃ after reacting for 1 hour, then adding 4 parts of urea, stopping the reaction after reacting for half an hour, and naturally cooling to obtain the A-stage phenolic resin.
Weighing 100g of A-stage phenolic resin, 3g of n-pentane, 1g of tween-80 and 8g of aluminum hydroxide, uniformly stirring, adding 8g of 2mol/L sulfuric acid solution, uniformly stirring again, placing in a mold, placing in an oven at 100 ℃, heating for 10min, taking out, cooling, and demolding to obtain a sample.
Does not carry out high-temperature roasting on cyanamide compounds to obtain C3N4The materials and other operations were the same as in example 1.
The apparent density of the sample obtained according to this method was determined to be 55kg/m3The thermal conductivity coefficient is 0.03W/mK, the oxygen index is 20, and the tensile strength is 0.075 MPa.
Comparative example 2
Weighing a certain amount of melamine, coating the melamine in an aluminum foil with micropores on the surface, placing the aluminum foil in a muffle furnace, roasting the melamine for 3 hours at 700 ℃, and naturally cooling to obtain C3N4And (5) producing the product.
Comparative example 3
Weighing a certain amount of urea, coating the urea in an aluminum foil with micropores on the surface, placing the aluminum foil in a muffle furnace, roasting the urea for 3 hours at 400 ℃, and naturally cooling to obtain C3N4And (5) producing the product.
Comparative example 4
2g of the above protonised C-containing compound are added in the curing step3N4The procedure of example 1 was otherwise the same as for the colloidal sulfuric acid solution of (1), to obtain a sample.
The apparent density of the sample is detected to be 49kg/m3The thermal conductivity coefficient is 0.024W/mK, the oxygen index is 24, the tensile strength is 0.10MPa, and the sample reaches the flame-retardant B1 grade.
Comparative example 5
30g of the above protonized C-containing compound were added in the curing step3N4The procedure of example 1 was otherwise the same as for the colloidal sulfuric acid solution of (1), to obtain a sample.
The apparent density of the sample is detected to be 60kg/m3The thermal conductivity coefficient is 0.028W/mK, the oxygen index is 20, the tensile strength is 0.08MPa, and the sample reaches the flame-retardant B1 grade.
Comparative example 6
The procedure is as in example 1. Weighing 100g of A-stage phenolic resin, 8g of n-pentane, 4g of tween-80 and 8g of aluminum hydroxide, uniformly stirring, and adding 8g of the protonized C-containing material3N4The colloidal sulfuric acid solution is stirred uniformly again, placed in a mold, placed in a drying oven at 100 ℃ for heating for 10min, taken out, cooled and demoulded.
The apparent density of the sample is detected to be 74kg/m3The thermal conductivity coefficient is 0.045W/mK, the oxygen index is 25, and the tensile strength is 0.15 MPa.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A preparation method of an in-situ nano modified phenolic resin building thermal insulation material is characterized by comprising the following steps:
s1, high-temperature roasting the cyanamide compound in the oxygen-deficient atmosphere to obtain C3N4A material;
s2, mixing C3N4Pretreating the material in acid to obtain protonized C3N4A colloidal solution;
s3, adding protonized C3N4The colloidal solution is used for curing an A-stage phenolic resin system to obtain the in-situ nano modified phenolic resin building thermal insulation material.
2. The method for preparing the in-situ nano modified phenolic resin building thermal insulation material as claimed in claim 1, wherein the cyanamide compound is one or more selected from dicyandiamide, melamine and urea.
3. The method for preparing the in-situ nano modified phenolic resin building thermal insulation material as claimed in claim 1, wherein the high temperature roasting is carried out at the temperature of 500-650 ℃ for 2-4 hours, and then the temperature is naturally reduced.
4. The method for preparing the in-situ nano modified phenolic resin building thermal insulation material as claimed in claim 1, wherein the acid is selected from one or more of sulfuric acid, phosphoric acid, phenolsulfonic acid and p-toluenesulfonic acid.
5. The method for preparing in-situ nano modified phenolic resin building thermal insulation material according to claim 1, wherein in step S2, the step C3N4The mass percentage of the material in the whole reaction system is 5-20%.
6. The method for preparing in-situ nano modified phenolic resin building thermal insulation material as claimed in claim 1, wherein the pretreatment is to mix C3N4The material is placed in the acid and stirred for 0.2-1 hour to obtain a transparent colloid acidic solution.
7. The method for preparing the in-situ nano modified phenolic resin building thermal insulation material as claimed in claim 1, wherein the step S3 further comprises the following steps:
s31, mixing phenol and paraformaldehyde, adding an alkaline catalyst, carrying out a polymerization reaction, and adding urea after the reaction is finished to obtain A-stage phenolic resin;
s32, converting the A-stage phenolic resin into protonized C3N4And (3) blending the colloidal solution, the foaming agent, the foam stabilizer and the reinforcing agent, and heating, foaming and curing to obtain the in-situ nano modified phenolic resin building thermal insulation material.
8. The method for preparing in-situ nano modified phenolic resin building thermal insulation material according to claim 7, wherein the method comprisesThe mass parts of the components in the step S32 are as follows: 80-100 parts of A-stage phenolic resin and protonated C3N45-20 parts of colloidal solution, 0.5-10 parts of curing agent, 0.5-5 parts of foaming agent, 0.1-3 parts of foam stabilizer and 1-20 parts of reinforcing agent.
9. The method for preparing the in-situ nano modified phenolic resin building thermal insulation material as claimed in claim 7, wherein the curing temperature is 50-120 ℃ and the curing time is 5-20 min.
10. An in-situ nano-modified phenolic resin building insulation material prepared by the method of any one of claims 1 to 9.
CN202010982580.4A 2020-09-17 2020-09-17 In-situ nano modified phenolic resin building thermal insulation material and preparation method thereof Active CN111909484B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007070508A (en) * 2005-09-08 2007-03-22 Nitto Boseki Co Ltd Phenol resin-foamed article and method for producing the same
CN107674370A (en) * 2016-05-12 2018-02-09 王尧尧 A kind of cable insulation material preparation method comprising modified alta-mud
CN108192275A (en) * 2018-01-17 2018-06-22 石家庄学院 A kind of manufacturing method of phenol-formaldehyde resin modified/composite foamed external-wall heat-insulation material of polysilicon acid aluminium dihydrogen phosphate

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007070508A (en) * 2005-09-08 2007-03-22 Nitto Boseki Co Ltd Phenol resin-foamed article and method for producing the same
CN107674370A (en) * 2016-05-12 2018-02-09 王尧尧 A kind of cable insulation material preparation method comprising modified alta-mud
CN108192275A (en) * 2018-01-17 2018-06-22 石家庄学院 A kind of manufacturing method of phenol-formaldehyde resin modified/composite foamed external-wall heat-insulation material of polysilicon acid aluminium dihydrogen phosphate

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