A kind of fire-resistant adhesive and its production method

Abstract

The present invention discloses a fire-resistant adhesive and a production method thereof, comprising the following steps: phenol, sodium hydroxide and water are put into a reactor, and the temperature is raised to 60°C; 1 / 6 of paraformaldehyde is put into the reactor, and the temperature in the reactor is controlled to be 75-95°C; and then the same amount of paraformaldehyde as the first time is put into the reactor at intervals for a certain period of time; the temperature in the reactor is controlled to be kept at 85-95°C for a certain period of time, and then the temperature is raised to 95-110°C for reaction; the temperature in the reactor is lowered to 55-60°C, and γ-aminopropyl triethoxysilane is slowly dripped into the reactor to obtain γ-aminopropyl triethoxysilane modified phenolic resin; the above-mentioned γ-aminopropyl triethoxysilane modified phenolic resin, water and inorganic refractory fiber are added to a stirring barrel, and after the first stirring, a silicon-containing inorganic filler is added, and after the second stirring, the material is discharged to obtain a fire-resistant adhesive. The present invention has the advantages of fire resistance and high bonding strength.

Description

Technical Field

[0001] The invention relates to the technical field of macromolecular organic compounds, and in particular to a fire-resistant adhesive and a production method thereof. Background Art

[0002] Central air conditioning ducts are generally made of thermal insulation sandwich panels. Central air conditioning ducts need to experience hot and cold cycles and withstand certain wind pressure during long-term use. Most adhesives on the market use polyurethane glue, glass glue and other adhesives with good tensile bonding strength, but low fire resistance. The state has clear regulations on the fire resistance of building insulation materials; phenolic resin adhesives have the advantages of good heat resistance and aging resistance, but their disadvantages are low bonding strength and poor toughness. The market needs a fire-resistant adhesive that is flame-retardant and has high bonding strength. Summary of the invention

[0003] In view of the above-mentioned shortcomings currently existing, the present invention provides a fire-resistant adhesive and a production method thereof, which has the advantages of fire resistance, flame retardancy, high bonding strength, etc.

[0004] In order to achieve the above object, the present invention provides a method for producing a fire-resistant adhesive, comprising the following raw materials and steps:

[0005] The raw materials include:

[0006] Phenol, paraformaldehyde, sodium hydroxide, γ-aminopropyltriethoxysilane, inorganic refractory fiber, silicon-containing inorganic filler and water;

[0007] The steps include:

[0008] Step 1: Add the prepared weight portions of phenol, sodium hydroxide and water into a reaction kettle, and stop heating after the temperature is raised to 60° C.; add 1 / 6 of the prepared weight portion of paraformaldehyde into the reaction kettle, and control the temperature in the reaction kettle to be 75-95° C.; and then add the same amount of paraformaldehyde as the first time into the reaction kettle for multiple times at intervals of 15-25 minutes;

[0009] Step 2: Control the temperature in the reactor at 85-95°C for 60-80 minutes, then raise the temperature to 95-110°C for reaction;

[0010] Step 3: lowering the temperature in the reaction kettle to 55-60° C., slowly dripping the prepared weight portion of γ-aminopropyltriethoxysilane into the reaction kettle within 30 minutes, and discharging the material to obtain γ-aminopropyltriethoxysilane modified phenolic resin;

[0011] Step 4: Add the above-mentioned γ-aminopropyltriethoxysilane modified phenolic resin, water and inorganic refractory fiber into a stirring barrel, add silicon-containing inorganic filler after the first stirring, and after the second stirring, discharge the material to obtain a refractory adhesive.

[0012] According to one aspect of the present invention, the raw material weight components of the γ-aminopropyltriethoxysilane modified phenolic resin are as follows:

[0013] 350-400 parts of phenol, 176-224 parts of paraformaldehyde, 1.5-2 parts of sodium hydroxide, 160-300 parts of water, and 6-8 parts of γ-aminopropyltriethoxysilane.

[0014] According to one aspect of the present invention, the raw material weight components of the refractory adhesive are as follows, in parts by weight:

[0015] 50-65 parts of γ-aminopropyltriethoxysilane modified phenolic resin, 100-125 parts of water, 150-173 parts of inorganic refractory fiber, and 200-230 parts of silicon inorganic filler.

[0016] According to one aspect of the present invention, in step 2, the reaction time is 60 minutes.

[0017] According to one aspect of the present invention, in step 3, the rate of slowly dripping into the reaction kettle is 0.5 to 1 drop / second.

[0018] Based on the same inventive concept, the present invention also provides a refractory adhesive prepared by the production method of the refractory adhesive.

[0019] Principle of the present invention:

[0020] The molecular structure of the base-catalyzed thermosetting phenolic resin of the present invention is shown in (1), and the molecular structure of γ-aminopropyltriethoxysilane (commonly known as silane coupling agent KH550) is shown in (2). During the generation (preparation) process, the amino group in the γ-aminopropyltriethoxysilane is hydrolyzed to form a weak base, and undergoes a dehydration condensation reaction with the phenolic hydroxyl group on the phenol molecule in the base-catalyzed thermosetting phenolic resin to connect; the ethoxysilane functional group in the γ-aminopropyltriethoxysilane is hydrolyzed to silanol group, and in order to reduce the reaction between silanol groups, the γ-aminopropyltriethoxysilane is slowly dripped.

[0021]

[0022]

[0023] Beneficial effects of the present invention:

[0024] The present invention prepares a γ-aminopropyltriethoxysilane-modified phenolic resin, and improves the bonding strength and toughness of the phenolic resin through the interaction between the silanol groups in the γ-aminopropyltriethoxysilane-modified phenolic resin and the silicon-containing inorganic filler and the inorganic refractory fiber. The resin has reinforcement and compatibility with the inorganic refractory fiber and the silicon-containing inorganic filler, the inorganic refractory fiber further improves the bonding and toughness of the adhesive, and the silicon-containing inorganic filler has fire resistance. DETAILED DESCRIPTION

[0025] In order to facilitate the understanding of the present invention, the present invention will be described more comprehensively and carefully in combination with preferred embodiments below, but the protection scope of the present invention is not limited to the following specific embodiments.

[0026] Unless otherwise defined, all professional terms used below have the same meanings as those generally understood by those skilled in the art. The professional terms used herein are only for the purpose of describing specific embodiments and are not intended to limit the scope of protection of the present invention.

[0027] Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present invention can be purchased from the market or prepared by existing methods.

[0028] In order to solve the shortcomings of the existing refractory adhesives, the inventors of the present application provide a method for producing a refractory adhesive, comprising the following raw materials and steps:

[0029] The raw materials include:

[0030] Phenol, paraformaldehyde, sodium hydroxide, γ-aminopropyltriethoxysilane, inorganic refractory fiber, silicon-containing inorganic filler and water;

[0031] The steps include:

[0032] Step 1: Add the prepared weight portions of phenol, sodium hydroxide and water into a reaction kettle, and stop heating after the temperature is raised to 60° C.; add 1 / 6 of the prepared weight portion of paraformaldehyde into the reaction kettle, and control the temperature in the reaction kettle to be 75-95° C.; and then add the same amount of paraformaldehyde as the first time into the reaction kettle for multiple times at intervals of 15-25 minutes;

[0033] Step 2: Control the temperature in the reactor at 85-95°C for 60-80 minutes, then raise the temperature to 95-110°C for reaction;

[0034] Step 3: lowering the temperature in the reaction kettle to 55-60° C., slowly dripping the prepared weight portion of γ-aminopropyltriethoxysilane into the reaction kettle within 30 minutes, and discharging the material to obtain γ-aminopropyltriethoxysilane modified phenolic resin;

[0035] Step 4: Add the above-mentioned γ-aminopropyltriethoxysilane modified phenolic resin, water and inorganic refractory fiber into a stirring barrel, add silicon-containing inorganic filler after the first stirring, and after the second stirring, discharge the material to obtain a refractory adhesive.

[0036] As an optional embodiment, the raw material weight components of the γ-aminopropyltriethoxysilane modified phenolic resin are as follows, in parts by weight:

[0037] 350-400 parts of phenol, 176-224 parts of paraformaldehyde, 1.5-2 parts of sodium hydroxide, 160-300 parts of water, and 6-8 parts of γ-aminopropyltriethoxysilane.

[0038] As an optional embodiment, the raw material weight components of the refractory adhesive are as follows, in parts by weight:

[0039] 50-65 parts of γ-aminopropyltriethoxysilane modified phenolic resin, 100-125 parts of water, 150-173 parts of inorganic refractory fiber, and 200-230 parts of silicon inorganic filler.

[0040] As an optional implementation, in step 2, the reaction time is 60 minutes.

[0041] As an optional implementation, in step 3, the rate of slowly dripping into the reaction kettle is 0.5 to 1 drop / second.

[0042] An embodiment of the present invention further provides a refractory adhesive prepared by the above-mentioned production method of the refractory adhesive.

[0043] The above introduces the specific implementation methods of the present application. In order to objectively illustrate the technical effects produced by the present application, the following examples and comparative examples will be used for description.

[0044] Example 1

[0045] A preparation method of γ-aminopropyltriethoxysilane modified phenolic resin:

[0046] (1) Prepare the backup materials in the following weight ratio:

[0047]

[0048]

[0049] (2) Add the phenol, sodium hydroxide and water prepared in step (1) into the reaction kettle, raise the temperature in the kettle to 60°C and then stop heating. Add 1 / 6 of the paraformaldehyde prepared in step (1) into the reaction kettle, and control the temperature in the kettle. The temperature control range is 75°C. After the first addition of paraformaldehyde into the reaction kettle, add another amount of paraformaldehyde equal to the first addition every 25 minutes, and add five times;

[0050] (3) The temperature in the reactor was controlled at 85°C for 80 min; then the temperature was raised to 95°C for 60 min;

[0051] (4) lowering the temperature in the reaction kettle to 55° C., slowly dripping (0.5 drops / second) the γ-aminopropyltriethoxysilane prepared in step (1) into the reaction kettle within 30 minutes, and discharging the material to obtain a finished γ-aminopropyltriethoxysilane-modified phenolic resin.

[0052] Example 2

[0053] A method for preparing a fire-resistant adhesive comprises the following steps:

[0054] (1) Prepare the backup materials in the following weight ratio:

[0055]

[0056] Wherein, the above-mentioned γ-aminopropyltriethoxysilane modified phenolic resin is prepared in Example 1;

[0057] (2) adding the γ-aminopropyltriethoxysilane modified phenolic resin prepared in step (1), water and inorganic refractory fiber into a stirring barrel and stirring for 30 minutes;

[0058] (3) Add the silicon-containing inorganic filler prepared in step (1) into a stirring barrel and stir for 30 minutes to obtain a finished refractory adhesive.

[0059] Example 3

[0060] A method for preparing a fire-resistant adhesive comprises the following steps:

[0061] (1) Prepare the backup materials in the following weight ratio:

[0062]

[0063]

[0064] Wherein, the above-mentioned γ-aminopropyltriethoxysilane modified phenolic resin is prepared in Example 1;

[0065] (2) adding the γ-aminopropyltriethoxysilane modified phenolic resin prepared in step (1), water and inorganic refractory fiber into a stirring barrel and stirring for 35 minutes;

[0066] (3) Add the silicon-containing inorganic filler prepared in step (1) into a stirring barrel and stir for 35 minutes to obtain a finished refractory adhesive.

[0067] Example 4

[0068] A method for preparing a fire-resistant adhesive comprises the following steps:

[0069] (1) Prepare the backup materials in the following weight ratio:

[0070]

[0071] Wherein, the above-mentioned γ-aminopropyltriethoxysilane modified phenolic resin is prepared in Example 1;

[0072] (2) adding the γ-aminopropyltriethoxysilane modified phenolic resin prepared in step (1), water and inorganic refractory fiber into a stirring barrel and stirring for 40 minutes;

[0073] (3) Add the silicon-containing inorganic filler prepared in step (1) into a stirring barrel and stir for 40 minutes to obtain a refractory adhesive product.

[0074] Comparative Example 1

[0075] The difference between this comparative example and Example 1 is that in step (4), a moderate amount of γ-aminopropyltriethoxysilane is added all at once. The other steps and parameters are the same as those in Example 1.

[0076] Comparative Example 2

[0077] The difference between this comparative example and Example 2 is that the γ-aminopropyltriethoxysilane-modified phenolic resin of Comparative Example 1 is added, and the other steps and parameters are the same as those of Example 2.

[0078] Comparative Example 3

[0079] The difference between this comparative example and Example 2 is that unmodified base-catalyzed thermosetting phenolic resin is added, and the other steps and parameters are the same as Example 2.

[0080] Performance testing and result analysis:

[0081] The fire-resistant adhesives prepared in Examples 2-4 and Comparative Examples 2-3 were tested for impact strength of the films made of each adhesive according to the standard GB / T1043.1-2008; and for tensile shear strength of each adhesive according to the standard GB 7124-2008. The specific results are shown in Table 1 below (rigid material to rigid material):

[0082] Table 1:

[0083]

[0084] As can be seen from Table 1, as the ratio of γ-aminopropyl triethoxysilane modified phenolic resin to silicon-containing filler increases, the tensile shear strength and impact strength of the adhesive increase; Comparative Example 2 uses a one-time addition of γ-aminopropyl triethoxysilane to modify the phenolic resin, and compared with the slow dripping method used in Example 2 of the present invention, the tensile shear strength and impact strength of the adhesive decrease; Comparative Example 3 adds unmodified phenolic resin, and compared with Example 2 of the present invention, the tensile shear strength and impact strength of the adhesive decrease significantly. This shows that the γ-aminopropyl triethoxysilane modified phenolic resin of the present invention can interact with inorganic refractory fibers and silicon-containing inorganic fillers, and significantly improves the bonding strength and toughness of the refractory adhesive.

[0085] The above is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by any technician familiar with the art within the technical scope disclosed in the present invention should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention shall be based on the protection scope of the claims.

Claims

1. A method for producing a refractory adhesive, characterized in that: The method comprises the following raw materials and steps: The raw materials include: Phenol, paraformaldehyde, sodium hydroxide, γ-aminopropyltriethoxysilane, inorganic refractory fiber, silicon-containing inorganic filler and water; The steps include: Step 1: Add the prepared weight portions of phenol, sodium hydroxide and water into a reaction kettle, and stop heating after the temperature is raised to 60° C.; add 1 / 6 of the prepared weight portion of paraformaldehyde into the reaction kettle, and control the temperature in the reaction kettle to be 75-95° C.; and then add the same amount of paraformaldehyde as the first time into the reaction kettle for multiple times at intervals of 15-25 minutes; Step 2: Control the temperature in the reactor at 85-95°C for 60-80 minutes, then raise the temperature to 95-110°C for reaction; Step 3: lowering the temperature in the reaction kettle to 55-60° C., slowly dripping the prepared γ-aminopropyltriethoxysilane in parts by weight into the reaction kettle within 30 minutes, and discharging the material to obtain γ-aminopropyltriethoxysilane-modified phenolic resin; wherein, in parts by weight, the raw material weight components of the γ-aminopropyltriethoxysilane-modified phenolic resin are: 350-400 parts of phenol, 176-224 parts of paraformaldehyde, 1.5-2 parts of sodium hydroxide, 160-300 parts of water, and 6-8 parts of γ-aminopropyltriethoxysilane; Step 4: Add the above-mentioned γ-aminopropyl triethoxysilane modified phenolic resin, water and inorganic refractory fiber into a stirring barrel, add the silicon-containing inorganic filler after the first stirring, and after the second stirring, discharge the material to obtain a refractory adhesive; wherein, in terms of weight parts, the weight components of the raw materials of the refractory adhesive are: 50-65 parts of γ-aminopropyl triethoxysilane modified phenolic resin, 100-125 parts of water, 150-173 parts of inorganic refractory fiber, and 200-230 parts of silicon-containing inorganic filler.

2. The method for producing a refractory adhesive according to claim 1, characterized in that: In step 2, the reaction time is 60 min.

3. The method for producing a fire-resistant adhesive according to claim 1, characterized in that: In step 3, the rate of slowly dripping into the reaction kettle is 0.5 to 1 drop / second.

4. A refractory adhesive prepared by the method for producing a refractory adhesive according to any one of claims 1 to 3.

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