High-strength modified epoxy structural adhesive for rubber cable and preparation method of high-strength modified epoxy structural adhesive

Abstract

The invention discloses a high-strength modified epoxy structural adhesive for a rubber cable and a preparation method of the high-strength modified epoxy structural adhesive, the structural adhesive is a component A and a component B, and the mass ratio of the component A to the component B is (1.5-3): 1; wherein the component A is prepared from the following components in parts by weight: 65 to 75 parts of high-strength modified epoxy resin, 20 to 30 parts of reinforcing filler, 0.1 to 0.5 part of coloring filler, 0 to 2 parts of silane coupling agent, 0.5 to 1 part of dispersing aid, 0.5 to 1 part of defoaming agent and 0.5 to 1 part of thixotropic agent; and the component B is a modified thiol curing agent. According to the structural adhesive disclosed by the invention, high-strength chemical bonding is formed between terpyridyl introduced into the high-strength modified epoxy resin and rubber, and the thiol curing agent has good compatibility with the rubber, so that high-strength bonding can be formed between the structural adhesive and a rubber cable, and the stability of a rubber cable interface is ensured; the cable connector can be used for connection of rubber cables in different application scenes such as conventional atmosphere, burying and seabed.

Description

Technical Field

[0001] The present invention relates to the technical field of chemical materials, and particularly relates to a high-strength modified epoxy structural adhesive for rubber cables and a preparation method thereof. Background Art

[0002] Rubber cables are widely used in various electrical equipment and long-distance signal transmission. According to the mechanical external force they bear, they are divided into three categories: light, medium, and heavy. Light cables are generally used in household appliances and small electric equipment, and are required to be soft, light, and have good bending performance; medium cables are generally used in industrial and agricultural electrification; heavy cables are used in port machinery, searchlights, large-scale hydraulic drainage and irrigation, etc. Medium and heavy cables generally require long-distance transmission or branched transmission, and the application environments usually include conventional atmosphere, buried, and underwater, etc. At the cable interface, a high-strength structural adhesive is required, which requires both high-strength connection performance and good sealing performance to ensure that the interface does not have adverse phenomena such as falling off and cracking.

[0003] Therefore, how to develop a high-strength structural adhesive for rubber cables with high bonding strength and excellent sealing performance is an important means to ensure the quality of cable signal and power transmission, and has significant economic and social benefits. Summary of the Invention

[0004] To overcome the above problems, the purpose of the present invention is to provide a high-strength modified epoxy structural adhesive for rubber cables with excellent bonding performance, which can meet the connection requirements of rubber cables in different application scenarios such as conventional atmosphere, buried, and underwater.

[0005] To achieve the above purpose, the present invention is realized through the following technical solutions:

[0006] The present invention provides a high-strength modified epoxy structural adhesive for rubber cables. This structural adhesive is a two-component material including component A and component B, and the mass ratio of component A to component B is (1.5 - 3):1;

[0007] Component A, by weight, includes the following raw materials:

[0008] 65 - 75 parts of high-strength modified epoxy resin, 20 - 30 parts of reinforcing filler, 0.1 - 0.5 parts of coloring filler, 0 - 2 parts of silane coupling agent, 0.5 - 1 part of dispersion aid, 0.5 - 1 part of defoaming agent, 0.5 - 1 part of thixotropic agent;

[0009] Component B is a modified mercaptan curing agent.

[0010] As a possible implementation manner, further, the structural formula of the high-strength modified epoxy resin is as follows:

[0011]

[0012] Among them, n is an integer from 1 to 10.

[0013] As a possible implementation manner, further, the structural formula of the modified mercaptan curing agent is as follows:

[0014]

[0015] Among them, R1 is an alkylene group with 6 to 10 an alkylene group with 6 to 8 carbon atoms, R2 is an alkylene group with 6 to 8 carbon atoms, R3 is an alkylene group with 6 to 9 carbon atoms, and R4 is an alkylene group with 7 to 9 carbon atoms.

[0016] As a possible implementation manner, further, the reinforcing filler is at least one of glass fiber, rubber powder, kaolin, and mica powder.

[0017] As a possible implementation manner, further, the coloring filler is at least one of graphite, carbon black, and iron oxide black.

[0018] As a possible implementation manner, further, the silane coupling agent is at least one of KH-550, KH-560, KH-570, KH-792, and DL602.

[0019] As a possible implementation manner, further, the dispersion aid is at least one of BYK110, 272S, BYK320, and 5100; the defoaming agent is at least one of 6800 and 6600; the thixotropic agent is at least one of polyamide wax and fumed silica.

[0020] The present invention also provides a preparation method of the high-strength modified epoxy structural adhesive for rubber cables as described above, including the following steps:

[0021] Step 1), weigh each raw material according to the formula of the component A in claim 1;

[0022] Step 2), place the high-strength modified epoxy resin in a dispersion tank, and then add the coloring filler, dispersion aid, defoaming agent, and thixotropic agent, and disperse at high speed until uniform;

[0023] Step 3), then sequentially add the reinforcing filler and the silane coupling agent to the dispersion tank, and disperse at high speed until the fineness is below 80 μm to obtain component A;

[0024] Step 4), mix component A and component B according to a weight ratio of (1.5 to 3):1, and stir well to obtain the high-strength modified epoxy structural adhesive.

[0025] As a possible implementation manner, further, in step 2), the materials are dispersed at high speed until uniform at a rotation speed of 1000 to 1200 r / min.

[0026] As a possible implementation, further, in step 3), the material is highly dispersed at a rotational speed of 1500 - 2000 r / min for 1 - 2 h until the fineness is below 80 μm.

[0027] In terms of the selection of epoxy resin in the present invention, high-strength modified epoxy resin is adopted, and terpyridine is grafted onto the side chain of the epoxy resin. Through the empty orbitals of the nitrogen atoms on terpyridine, the adhesion strength on the surface of the rubber substrate is improved; in terms of the selection of the curing agent, modified mercaptan curing agent is adopted, thereby introducing sulfur elements into the resin system to improve the compatibility and adhesion with the rubber substrate. Sulfur elements are introduced into the resin system to improve the compatibility and adhesion with the rubber substrate. Combining the above improved technologies, the compatibility and adhesion between the epoxy structural adhesive and the rubber substrate are further improved.

[0028] The beneficial effects of the present invention are as follows:

[0029] 1) Based on the terpyridine introduced in the high-strength modified epoxy resin in the present invention, through the coordination of the nitrogen atoms in terpyridine, a high-strength bond with the rubber is achieved. At the same time, mercaptan curing agent is adopted, which contains more sulfur atoms and has good compatibility with vulcanized rubber. Therefore, the epoxy structural adhesive of the present invention has high-strength adhesion with the rubber cable, ensuring the stability of the rubber cable interface.

[0030] Specifically, the present invention selects terpyridine to be grafted onto the side chain of the epoxy resin by a one-step method to obtain high-strength modified epoxy resin. β-mercaptopropionic acid, pentaerythritol, toluene and a catalyst are used to obtain pentaerythritol tetrakis(mercaptoacetate) by vacuum distillation, and then a chain extension reaction is carried out with the epoxy resin at an appropriate temperature to obtain the mercaptan curing agent. At the same time, glass fibers are introduced into the structural adhesive formula, and the structural stability of the structural adhesive is improved by using the disordered extension and strengthening characteristics of the glass fibers; rubber powder is introduced, and the interfacial bonding strength is improved by using the compatibility between the rubber powder and the rubber cable.

[0031] 2) The silane coupling agent selected in the present invention can effectively enhance the compatibility between the resin and the filler, ensure the stable dispersion of reinforcing fillers such as glass fibers and rubber powder, and maximize the mechanical strength of the structural adhesive and the interfacial bonding force with the rubber cable. At the same time, the silane coupling agent can improve the reaction rate of the material at low temperature and achieve rapid curing at room temperature. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for the description of the embodiments or the prior art. Obviously, the drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts.

[0033] Figure 1 Schematic diagram of bonding of rubber cable prepared in Example 2;

[0034] Figure 2 State diagram of the high-strength structural adhesive-bonded rubber cable joint prepared in Example 2 after being subjected to a strong force;

[0035] Figure 3 State diagram of the structural adhesive-bonded rubber cable joint prepared in Comparative Example 1 after being subjected to a strong force;

[0036] Figure 4 State diagram of the structural adhesive-bonded rubber cable joint prepared in Comparative Example 2 after being subjected to a strong force. Detailed implementation manners

[0037] To make the objectives, technical solutions and advantages of the embodiments of the present invention clearer, 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 are some, rather than all, of the embodiments of the present invention. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without making creative efforts shall fall within the protection scope of the present invention.

[0038] The present invention provides a high-strength modified epoxy structural adhesive for rubber cables. The structural adhesive is a two-component material, including component A and component B, and the mass ratio of component A to component B is (1.5 - 3):1;

[0039] Among them, component A, by weight, includes: 65 - 75 parts of high-strength modified epoxy resin, 20 - 30 parts of reinforcing filler, 0.1 - 0.5 parts of coloring filler, 0 - 2 parts of silane coupling agent, 0.5 - 1 part of dispersion aid, 0.5 - 1 part of defoaming agent, and 0.5 - 1 part of thixotropic agent. Component B is a modified thiol curing agent.

[0040] The structural formula of the high-strength modified epoxy resin is as follows:

[0041]

[0042] Among them, n takes an integer from 1 to 10.

[0043] The structural formula of the modified thiol curing agent is as follows:

[0044]

[0045] Among them, R1 is C6 - C 10R1 is an alkylene group with 6 to 8 carbon atoms, R2 is an alkylene group with 6 to 8 carbon atoms, R3 is an alkylene group with 6 to 9 carbon atoms, and R4 is an alkylene group with 7 to 9 carbon atoms. Among them, the alkylene group represents a straight-chain alkane. For example, C6 represents -CH2CH2CH2CH2CH2CH2-, C7 represents -CH2CH2CH2CH2CH2CH2CH2-, and so on. By comprehensively adjusting the carbon chain length of the alkylene group, curing agents with different hydrophobic properties can be obtained to meet the waterproof performance requirements of the cable.

[0046] The above-mentioned reinforcing filler is at least one of glass fiber, rubber powder, kaolin, and mica powder; the coloring filler is at least one of graphite, carbon black, and iron oxide black; the silane coupling agent is at least one of KH-550, KH-560, KH-570, KH-792, and DL602; the dispersion aid is at least one of BYK110, 272S, BYK320, and 5100; the defoaming agent is at least one of 6800 and 6600; the thixotropic agent is at least one of polyamide wax and fumed silica.

[0047] The formulations of the following Examples 1-3 are shown in Table 1 below:

[0048] Table 1

[0049]

[0050] Example 1

[0051] In this example, the preparation method of the high-strength modified epoxy structural adhesive for rubber cables includes the following steps:

[0052] Step 1), Weigh each raw material according to the weight parts of the formulation of Group A in Example 1 in Table 1.

[0053] Step 2), Place the high-strength modified epoxy resin in a dispersion tank, and then add the coloring filler, dispersion aid, defoaming agent, and thixotropic agent, and disperse them at a high speed of 1000 r / min until uniform.

[0054] Step 3), Then add the reinforcing filler and silane coupling agent to the dispersion tank in sequence, and disperse them at a high speed of 1500 r / min until the fineness is below 80 μm to obtain Component A.

[0055] Step 4), Mix Component A and Component B according to a weight ratio of 1.5:1, and stir them evenly to obtain the high-strength epoxy structural adhesive.

[0056] Example 2

[0057] In this example, the preparation method of the high-strength modified epoxy structural adhesive for rubber cables includes the following steps:

[0058] Step 1): Weigh each raw material according to the weight parts in the formulation of Group A in Example 2 of Table 1.

[0059] Step 2): Place the high-strength modified epoxy resin in a dispersion tank, then add the coloring filler, dispersion aid, defoaming agent, and thixotropic agent, and disperse at a high speed of 1100 r / min until uniform.

[0060] Step 3): Then, add the reinforcing filler and silane coupling agent to the dispersion tank in sequence, and disperse at a high speed of 1800 r / min until the fineness is below 80 μm to obtain Component A.

[0061] Step 4): Mix Component A and Component B according to a weight ratio of 2:1, and stir well to obtain the high-strength epoxy structural adhesive.

[0062] Appendix Figure 2 It is a photo of the structural adhesive in Example 2. It can be found that after the structural adhesive in Example 2 is cured, there is a strong bond between the structural adhesive and the rubber cable, and it remains intact under the strong force of more than 15 MPa, meeting the usage requirements.

[0063] Example 3

[0064] The preparation method of the high-strength modified epoxy structural adhesive for rubber cables in this example includes the following steps:

[0065] Step 1): Weigh each raw material according to the weight parts in the formulation of Group A in Example 3 of Table 1.

[0066] Step 2): Place the high-strength modified epoxy resin in a dispersion tank, then add the coloring filler, dispersion aid, defoaming agent, and thixotropic agent, and disperse at a high speed of 1200 r / min until uniform.

[0067] Step 3): Then, add the reinforcing filler and silane coupling agent to the dispersion tank in sequence, and disperse at a high speed of 2000 r / min until the fineness is below 80 μm to obtain Component A.

[0068] Step 4): Mix Component A and Component B according to a weight ratio of 3:1, and stir well to obtain the high-strength epoxy structural adhesive.

[0069] Comparative Example 1

[0070] Mix the Component A in Example 2 with the commercially available amide curing agent 2792 to prepare a sample as Comparative Example 1. Appendix Figure 3 It is a photo of the structural adhesive in Comparative Example 1. It can be found that after the structural adhesive in Comparative Example 1 is cured, it is prone to peeling under the strong force of 10 MPa, and the strength is not high, unable to meet the usage requirements.

[0071] Comparative Example 2

[0072] Replace the high-strength modified epoxy resin in Component A of Example 2 with conventional 6101 epoxy resin, while keeping other components unchanged. The curing agent used remains the same, which is a thiol curing agent (R1 is C6, R2 is C7, R3 is C8, R4 is C9), serving as Comparative Example 2. Attached Figure 4 The photo of the structural adhesive of Comparative Example 2 is shown. It can be found that after the structural adhesive of Comparative Example 2 is cured, it falls off under the strong force of 8 MPa, with low strength and cannot meet the usage requirements.

[0073] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: they can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements on some of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A high-strength modified epoxy structural adhesive for rubber cables, characterized in that: It comprises a component A and a component B, wherein the mass ratio of the component A to the component B is (1.5-3):1; The component A comprises the following raw materials in parts by weight: 65-75 parts of high-strength modified epoxy resin, 20-30 parts of reinforcing filler, 0.1-0.5 parts of colored filler, 0-2 parts of silane coupling agent, 0.5-1 parts of dispersing aid, 0.5-1 parts of defoaming agent, 0.5-1 parts of thixotropic agent; The component B is a modified mercaptan curing agent.

2. The high-strength modified epoxy structural adhesive for rubber cable according to claim 1, characterized in that: The structural formula of the high-strength modified epoxy resin is as follows: Here, n is an integer from 1 to 10.

3. The high-strength modified epoxy structural adhesive for rubber cable according to claim 1, characterized in that: The structural formula of the modified mercaptan curing agent is as follows: Where R1 is C6-C 10 R2 is a C6-C8 alkylene group, R3 is a C6-C9 alkylene group, and R4 is a C7-C9 alkylene group.

4. The high-strength modified epoxy structural adhesive for rubber cable according to claim 1, characterized in that: The reinforcing filler is at least one of glass fiber, rubber powder, kaolin and mica powder.

5. The high-strength modified epoxy structural adhesive for rubber cable according to claim 1, characterized in that: The coloring filler is at least one of graphite, carbon black and black iron oxide.

6. The high-strength modified epoxy structural adhesive for rubber cable according to claim 1, characterized in that: The silane coupling agent is at least one of KH-550, KH-560, KH-570, KH-792 and DL602.

7. The high-strength modified epoxy structural adhesive for rubber cable according to claim 1, characterized in that: The dispersing aid is at least one of BYK110, 272S, BYK320 and 5100; the defoaming agent is at least one of 6800 and 6600; and the thixotropic agent is at least one of polyamide wax and fumed silica.

8. A method for preparing a high-strength modified epoxy structural adhesive for rubber cables as claimed in any one of claims 1 to 7, characterized in that: The following steps are involved: Step 1), weighing each raw material according to the formula of component A in claim 1; Step 2), placing the high-strength modified epoxy resin in a dispersion tank, adding a coloring filler, a dispersing aid, a defoaming agent, and a thixotropic agent, and dispersing at high speed until uniform; Step 3), adding reinforcing filler and silane coupling agent to the dispersion tank in sequence, and dispersing at high speed until the fineness is less than 80 μm to obtain component A; Step 4), component A and component B are mixed in a weight ratio of (1.5-3):1, and stirred thoroughly to obtain a high-strength modified epoxy structural adhesive.

9. The method for preparing the high-strength modified epoxy structural adhesive for rubber cable according to claim 8, characterized in that: In step 2), the material is dispersed at a high speed of 1000-1200 r / min until it is uniform.

10. The method for preparing the high-strength modified epoxy structural adhesive for rubber cables according to claim 8, characterized in that: In step 3), the material is dispersed at a high speed of 1500-2000 r / min for 1-2 hours until the fineness is less than 80 μm.

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