A room-temperature adhesive for prefabricated rubber sports fields and its preparation method

Abstract

The invention relates to a room-temperature adhesive for a prefabricated rubber court and a preparation method thereof, belonging to the field of epoxy resin adhesives. The adhesive comprises, by weight, 100 parts of epoxy resin, 20-30 parts of a toughening agent, 10-15 parts of a reinforcing agent, 35-50 parts of a curing agent, 3-5 parts of a curing accelerator, 10-15 parts of a diluent, 10-15 parts of an inorganic filler, and 2-3 parts of a thixotropic agent. The silane coupling agent structure in the reinforcing agent can couple with the inorganic filler to improve the compatibility of the inorganic filler with an epoxy resin matrix, and the multi-branched terminal amino structure in the reinforcing agent can react with the epoxy group in the epoxy resin. The reinforcing agent connects the epoxy resin matrix together, and the energy generated by an external force can be uniformly dispersed to other epoxy resin matrix molecular chains through the reinforcing agent, thereby dispersing the stress acting on the epoxy resin matrix, effectively alleviating the stress concentration phenomenon, and further reinforcing the toughening effect.

Description

Technical Field

[0001] The invention belongs to the field of epoxy resin adhesives, and in particular relates to a room temperature adhesive for a prefabricated rubber court and a preparation method thereof. Background Art

[0002] Prefabricated rubber courts are a type of sports ground surface made of prefabricated rubber material. They are widely used in indoor and outdoor sports venues such as schools, stadiums, and community fitness centers to meet people's growing demand for physical fitness. Prefabricated rubber courts are characterized by their unique wear resistance, anti-slip, and shock absorption properties, providing athletes with a safe and comfortable sports environment. The molded product is composed of two layers with concave and convex patterns, which maximizes the anchoring density between the runway material and the base surface while reducing the impact during exercise.

[0003] Use the matching adhesive to directly stick the paving runway membrane on the dense foundation. Epoxy resin adhesive has good bonding properties, mechanical properties, electrical insulation, chemical stability, low shrinkage, easy processing and molding, etc. It is widely used in the field of room temperature adhesives. However, when pure epoxy resin adhesive reacts with the curing agent, it will react to form a complex three-dimensional network structure. In addition, the epoxy resin itself has strong cohesion, and after curing, it has the disadvantages of greater brittleness and insufficient toughness.

[0004] In traditional technology, external toughening agents are usually added to improve the shortcomings of epoxy resin's insufficient toughness. For example, the introduction of macromolecules containing flexible chain segments can improve the impact toughness of epoxy resin. However, with the introduction of flexible macromolecular segments, the cross-linking density of epoxy resin is reduced, which improves toughness while also reducing its mechanical strength. Summary of the Invention

[0005] In order to solve the technical problems mentioned in the background technology, the purpose of the present invention is to provide a room temperature adhesive for prefabricated rubber courts and a preparation method thereof;

[0006] The purpose of the present invention can be achieved through the following technical solutions:

[0007] A room temperature adhesive for a prefabricated rubber court comprises the following raw materials in parts by weight:

[0008] 100 parts of epoxy resin, 20-30 parts of toughening agent, 10-15 parts of reinforcing agent, 35-50 parts of curing agent, 3-5 parts of curing accelerator, 10-15 parts of diluent, 10-15 parts of inorganic filler and 2-3 parts of thixotropic agent;

[0009] The reinforcing agent is prepared by the following method:

[0010] Step A1: 4-hydroxyisophthalaldehyde, 2,4-dinitroaniline, acetic acid, and benzene were mixed and added to a reaction kettle. The stirring reaction rate was controlled at 200-300 r / min. The temperature was raised to 75-85°C. The mixture was stirred and reacted for 3-4 hours, and then vacuum rotary evaporation was performed to obtain intermediate 1.

[0011] Furthermore, the ratio of 4-hydroxyisophthalaldehyde, 2,4-dinitroaniline, acetic acid and benzene is 0.1 mol: 0.2 mol: 3-5 g: 100 mL;

[0012] In step A1, the aldehyde group in 4-hydroxyisophthalaldehyde reacts with the amino group in 2,4-dinitroaniline to graft 2,4-dinitroaniline onto 4-hydroxyisophthalaldehyde. The structural formula is shown below:

[0013]

[0014] Step A2: Intermediate 1, sodium carbonate, and DMF were mixed and added to a reactor. The stirring reaction rate was controlled at 300-400 r / min. The temperature was raised to 95-110°C. After stirring at this temperature for 20 minutes, 3-chloropropyltriethoxysilane was added. The mixture was then stirred at this temperature for 5-6 hours. The mixture was washed with deionized water 3-4 times and dried to obtain Intermediate 2.

[0015] Furthermore, the ratio of the intermediate 1, 3-chloropropyltriethoxysilane, sodium carbonate and DMF is 0.1 mol: 0.1 mol: 5-6 g: 150 mL;

[0016] In step A2, intermediate 1 reacts with sodium hydroxide to generate sodium phenolate, which is then reacted with 3-chloropropyltriethoxysilane to graft the silane coupling agent onto the intermediate 1 molecule. The structural formula is shown below:

[0017]

[0018] Step A3: Mix the intermediate 2, ammonium sulfide, and benzene and add them to a reactor. Control the stirring reaction rate to be 150-300 r / min, raise the temperature to 65-75°C, keep stirring and react for 2-3 hours, and then vacuum rotary evaporate to obtain the reinforcing agent.

[0019] Furthermore, the ratio of intermediate 2, ammonium sulfide and benzene is 0.1 mol: 50 mL: 200 mL;

[0020] In step A3, the nitro group is reduced to an amino group under the reducing action of amine sulfide, introducing a multi-branched amino structure. The specific structure is shown below:

[0021]

[0022] A method for preparing a room temperature adhesive for a prefabricated rubber court is prepared by the following steps:

[0023] The epoxy resin, reinforcing agent, diluent, inorganic filler and thixotropic agent were mixed and added into a high-powered mixer. After strong stirring for 2 hours, the toughening agent, curing agent and curing accelerator were added. The mixture was stirred for another 2 hours and then cured at room temperature for 6 hours to obtain a room-temperature adhesive.

[0024] Beneficial effects of the present invention:

[0025] The present invention discloses a room-temperature adhesive for a prefabricated rubber court. The room-temperature adhesive takes an epoxy resin as a matrix and is blended with a reinforcing agent. Compared with traditional epoxy resin adhesives, the room-temperature adhesive increases the toughness of the adhesive while improving its mechanical strength. The silane coupling agent structure in the reinforcing agent can couple with an inorganic filler, thereby improving the compatibility of the inorganic filler with the epoxy resin matrix. The multi-branched terminal amino structure in the reinforcing agent can react with the epoxy group in the epoxy resin. The reinforcing agent connects the epoxy resin matrix together. The energy generated by external force can be evenly dispersed to other epoxy resin matrix molecular chains through the reinforcing agent, thereby dispersing the stress acting on the epoxy resin matrix, effectively alleviating stress concentration, and further enhancing the toughening effect. DETAILED DESCRIPTION

[0026] 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 embodiments described 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 making any creative efforts shall fall within the scope of protection of the present invention.

[0027] Example 1

[0028] The specific implementation method of preparing a room temperature adhesive for a prefabricated rubber court in this embodiment is as follows:

[0029] 1) Preparation of reinforcing agent

[0030] a1: 4-Hydroxyisophthalaldehyde, 2,4-dinitroaniline, acetic acid, and benzene were mixed and added to a reactor. The stirring reaction rate was controlled at 200 r / min. The temperature was raised to 75°C. The mixture was stirred and reacted for 3 h, and then vacuum rotary evaporation was performed to obtain intermediate 1. In the above reaction, the ratio of 4-Hydroxyisophthalaldehyde, 2,4-dinitroaniline, acetic acid, and benzene was 0.1 mol:0.2 mol:3 g:100 mL.

[0031] a2: Intermediate 1, sodium carbonate, and DMF were mixed and added to a reactor. The stirring reaction rate was controlled at 300 r / min, and the temperature was raised to 95°C. After stirring for 20 minutes, 3-chloropropyltriethoxysilane was added. The mixture was then stirred for 5 hours, washed three times with deionized water, and dried to obtain intermediate 2. In the above reaction, the ratio of intermediate 1, 3-chloropropyltriethoxysilane, sodium carbonate, and DMF was 0.1 mol: 0.1 mol: 5 g: 150 mL.

[0032] a3: Mix the intermediate 2, ammonium sulfide, and benzene and add them to a reactor. Control the stirring reaction rate at 150 r / min, raise the temperature to 65°C, keep stirring and react for 2 hours, and then evaporate under reduced pressure to obtain the reinforcing agent. In the above reaction, the ratio of intermediate 2, ammonium sulfide, and benzene is 0.1 mol:50 mL:200 mL.

[0033] 2) Preparation of room temperature adhesive for prefabricated rubber courts

[0034] s1: Weigh 100 parts of epoxy resin (E-51 epoxy resin is used in both the present embodiment and the comparative example), 20 parts of toughening agent (carboxyl-terminated nitrile rubber is used in both the present embodiment and the comparative example), 35 parts of curing agent (dicyandiamide is used in both the present embodiment and the comparative example), 10 parts of reinforcing agent, 3 parts of curing accelerator (imidazole is used in both the present embodiment and the comparative example), 10 parts of diluent (phenyl glycidyl ether is used in both the present embodiment and the comparative example), 10 parts of inorganic filler (graphene of Shanghai MacLean Biochemical Technology Co., Ltd. is used in both the present embodiment and the comparative example, model S992592) and 2 parts of thixotropic agent (fumed silica of Shanghai Aladdin Biochemical Technology Co., Ltd. is used in both the present embodiment and the comparative example, model S104600);

[0035] s2: Mix the epoxy resin, reinforcing agent, diluent, inorganic filler and thixotropic agent into a high-powered mixer, stir vigorously for 2 hours, then add the toughening agent, curing agent and curing accelerator, continue stirring for 2 hours, and cure at room temperature for 6 hours to obtain a room-temperature adhesive.

[0036] Example 2

[0037] The specific implementation method of preparing a room temperature adhesive for a prefabricated rubber court in this embodiment is as follows:

[0038] 1) Preparation of toughening modifier

[0039] a1: 4-Hydroxyisophthalaldehyde, 2,4-dinitroaniline, acetic acid, and benzene were mixed and added to a reactor. The stirring reaction rate was controlled at 250 r / min. The temperature was raised to 80°C. After stirring and reacting for 4 hours, the mixture was evaporated under reduced pressure to obtain intermediate 1. In the above reaction, the ratio of 4-Hydroxyisophthalaldehyde, 2,4-dinitroaniline, acetic acid, and benzene was 0.1 mol:0.2 mol:4 g:100 mL.

[0040] a2: Intermediate 1, sodium carbonate, and DMF were mixed and added to a reactor. The stirring reaction rate was controlled at 350 r / min. The temperature was raised to 100°C, and 3-chloropropyltriethoxysilane was added after being kept warm and stirred for 20 minutes. The mixture was then kept warm and stirred for 6 hours, washed three times with deionized water, and dried to obtain intermediate 2. In the above reaction, the amount ratio of intermediate 1, 3-chloropropyltriethoxysilane, sodium carbonate, and DMF was 0.1 mol: 0.1 mol: 5.5 g: 150 mL.

[0041] a3: Mix the intermediate 2, ammonium sulfide, and benzene in a reactor, control the stirring reaction rate to 200 r / min, heat to 70°C, keep stirring and react for 2 hours, and then vacuum rotary evaporate to obtain the reinforcing agent; in the above reaction, the amount ratio of intermediate 2, ammonium sulfide, and benzene is 0.1 mol:50 mL:200 mL;

[0042] 2) Preparation of room temperature adhesive for prefabricated rubber courts

[0043] s1: Weigh 100 parts of epoxy resin, 25 parts of toughening agent, 12 parts of reinforcing agent, 40 parts of curing agent, 4 parts of curing accelerator, 12 parts of diluent, 12 parts of inorganic filler and 2 parts of thixotropic agent according to weight;

[0044] s2: Mix the epoxy resin, reinforcing agent, diluent, inorganic filler and thixotropic agent into a high-powered mixer, stir vigorously for 2 hours, then add the toughening agent, curing agent and curing accelerator, continue stirring for 2 hours, and cure at room temperature for 6 hours to obtain a room-temperature adhesive.

[0045] Example 3

[0046] The specific implementation method of preparing a room temperature adhesive for a prefabricated rubber court in this embodiment is as follows:

[0047] 1) Preparation of toughening modifier

[0048] a1: 4-Hydroxyisophthalaldehyde, 2,4-dinitroaniline, acetic acid, and benzene were mixed and added to a reactor. The stirring reaction rate was controlled at 300 r / min. The temperature was raised to 85°C. After stirring and reacting for 4 hours, the mixture was evaporated under reduced pressure to obtain intermediate 1. In the above reaction, the ratio of 4-Hydroxyisophthalaldehyde, 2,4-dinitroaniline, acetic acid, and benzene was 0.1 mol:0.2 mol:5 g:100 mL.

[0049] a2: Intermediate 1, sodium carbonate, and DMF were mixed and added to a reactor. The stirring reaction rate was controlled at 400 r / min. The temperature was raised to 105°C, and 3-chloropropyltriethoxysilane was added after being kept warm and stirred for 20 minutes. The mixture was then kept warm and stirred for 6 hours. The mixture was washed three times with deionized water and dried to obtain intermediate 2. In the above reaction, the ratio of intermediate 1, 3-chloropropyltriethoxysilane, sodium carbonate, and DMF was 0.1 mol: 0.1 mol: 6 g: 150 mL.

[0050] a3: Mix the intermediate 2, ammonium sulfide, and benzene and add them to a reactor. Control the stirring reaction rate at 250 r / min, raise the temperature to 75°C, keep stirring and react for 2 hours, and then evaporate under reduced pressure to obtain the reinforcing agent. In the above reaction, the ratio of intermediate 2, ammonium sulfide, and benzene is 0.1 mol:50 mL:200 mL.

[0051] 2) Preparation of room temperature adhesive for prefabricated rubber courts

[0052] s1: Weigh 100 parts of epoxy resin, 13 parts of reinforcing agent, 26 parts of toughening modifier, 45 parts of curing agent, 5 parts of curing accelerator, 13 parts of diluent, 13 parts of inorganic filler and 3 parts of thixotropic agent according to weight;

[0053] s2: Mix the epoxy resin, reinforcing agent, diluent, inorganic filler and thixotropic agent into a high-powered mixer, stir vigorously for 2 hours, then add the toughening agent, curing agent and curing accelerator, continue stirring for 2 hours, and cure at room temperature for 6 hours to obtain a room-temperature adhesive.

[0054] Example 4

[0055] The specific implementation method of preparing a room temperature adhesive for a prefabricated rubber court in this embodiment is as follows:

[0056] 1) Preparation of toughening modifier

[0057] a1: 4-Hydroxyisophthalaldehyde, 2,4-dinitroaniline, acetic acid, and benzene were mixed and added to a reactor. The stirring reaction rate was controlled at 300 r / min. The temperature was raised to 85°C. After stirring and reacting for 4 hours, the mixture was evaporated under reduced pressure to obtain intermediate 1. In the above reaction, the ratio of 4-Hydroxyisophthalaldehyde, 2,4-dinitroaniline, acetic acid, and benzene was 0.1 mol:0.2 mol:5 g:100 mL.

[0058] a2: Intermediate 1, sodium carbonate, and DMF were mixed and added to a reactor. The stirring reaction rate was controlled at 400 r / min. The temperature was raised to 110°C, and 3-chloropropyltriethoxysilane was added after being kept warm and stirred for 20 minutes. The mixture was then kept warm and stirred for 6 hours, washed three times with deionized water, and dried to obtain intermediate 2. In the above reaction, the ratio of intermediate 1, 3-chloropropyltriethoxysilane, sodium carbonate, and DMF was 0.1 mol: 0.1 mol: 6 g: 150 mL.

[0059] a3: Mix the intermediate 2, ammonium sulfide, and benzene in a reactor, control the stirring reaction rate to 300 r / min, raise the temperature to 75°C, keep stirring and react for 2 hours, and then evaporate under reduced pressure to obtain the reinforcing agent; in the above reaction, the amount ratio of intermediate 2, ammonium sulfide, and benzene is 0.1 mol:50 mL:200 mL;

[0060] 2) Preparation of room temperature adhesive for prefabricated rubber courts

[0061] s1: Weigh 100 parts of epoxy resin, 15 parts of reinforcing agent, 30 parts of toughening modifier, 50 parts of curing agent, 5 parts of curing accelerator, 15 parts of diluent, 15 parts of inorganic filler and 3 parts of thixotropic agent according to weight;

[0062] s2: Mix the epoxy resin, reinforcing agent, diluent, inorganic filler and thixotropic agent into a high-powered mixer, stir vigorously for 2 hours, then add the toughening agent, curing agent and curing accelerator, continue stirring for 2 hours, and cure at room temperature for 6 hours to obtain a room-temperature adhesive.

[0063] Comparative Example 1

[0064] The difference between this comparative example and Example 3 is that no reinforcing agent is added;

[0065] Comparative Example 2

[0066] This comparative example uses a cardanol glycidyl ether modified epoxy resin adhesive prepared in Example 5 of Chinese patent CN108611036A;

[0067] The room temperature adhesives prepared in Examples 1-4 and Comparative Examples 1-2 were subjected to tensile strength tests, impact strength tests, and T-peel strength tests in accordance with GB / T7124-2008, GB / T2567-2008, and GB / T2791-1995. Specific test data are shown in Table 1.

[0068] Table 1

[0069]

[0070] From the data in Table 1, it can be seen that the room temperature adhesives prepared in Examples 1-4 have a tensile strength of 22.4-24.3 MPa and an impact strength of 17.2-19.5 KJ / m 2 The T-peel strength is 4.2-5.4 KN / m, which is significantly better than the adhesive prepared in Comparative Examples 1-2. This shows that the room temperature adhesive for rubber courts prepared in this embodiment has not only good tensile strength, but also good impact resistance.

[0071] Throughout the specification, references to terms such as "one embodiment," "example," and "specific example" indicate that the specific features, structures, materials, or characteristics described in conjunction with that embodiment or example are included in at least one embodiment or example of the present invention. In this specification, schematic representations of these terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

[0072] 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 described specific embodiments or replace them in similar ways. As long as they do not deviate from the invention or exceed the scope defined by the claims, they should all fall within the scope of protection of the present invention.

Claims

1. A room temperature adhesive for prefabricated rubber courts, characterized in that: The composition comprises, by weight, 100 parts of epoxy resin, 20-30 parts of toughening agent, 10-15 parts of reinforcing agent, 35-50 parts of curing agent, 3-5 parts of curing accelerator, 10-15 parts of diluent, 10-15 parts of inorganic filler and 2-3 parts of thixotropic agent; The reinforcing agent is prepared by the following method: Step A1: 4-hydroxyisophthalaldehyde, 2,4-dinitroaniline, acetic acid and benzene were mixed and added, the temperature was raised to 75-85°C, the mixture was stirred and reacted for 3-4 hours, and then vacuum evaporated to obtain intermediate 1; Step A2: Intermediate 1, sodium carbonate and DMF were mixed and heated to 95-110°C. After stirring for 20 minutes, 3-chloropropyltriethoxysilane was added. The mixture was stirred for 5-6 hours, washed with deionized water 3-4 times and dried to obtain Intermediate 2. Step A3: Mix the intermediate 2, ammonium sulfide, and benzene, raise the temperature to 65-75°C, stir and react for 2-3 hours, and then evaporate under reduced pressure to obtain the reinforcing agent; In step A1, the ratio of 4-hydroxyisophthalaldehyde, 2,4-dinitroaniline, acetic acid and benzene is 0.1 mol:0.2 mol:3-5 g:100 mL; In step A2, the ratio of intermediate 1, 3-chloropropyltriethoxysilane, sodium carbonate and DMF is 0.1 mol: 0.1 mol: 5-6 g: 150 mL; In step A3, the usage ratio of intermediate 2, ammonium sulfide and benzene is 0.1 mol:50 mL:200 mL.

2. The method for preparing a room temperature adhesive for a prefabricated rubber court according to claim 1, characterized in that: Made by the following steps: The epoxy resin, reinforcing agent, diluent, inorganic filler and thixotropic agent were mixed and added into a high-powered mixer. After strong stirring for 2 hours, the toughening agent, curing agent and curing accelerator were added. The mixture was stirred for another 2 hours and then cured at room temperature for 6 hours to obtain a room-temperature adhesive.

3. The method for preparing a room temperature adhesive for a prefabricated rubber court according to claim 2, characterized in that: Graphene is selected as the inorganic filler.

4. The method for preparing a room temperature adhesive for a prefabricated rubber court according to claim 3, characterized in that: The curing agent is dicyandiamide.

5. The method for preparing a room temperature adhesive for a prefabricated rubber court according to claim 4, characterized in that: Imidazole is used as the accelerator.

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