High-performance wide-temperature-range epoxy resin binder and preparation method thereof

Abstract

The invention relates to a high-performance wide-temperature-range epoxy resin binder and a preparation method thereof, and belongs to the technical field of epoxy resin binders. The high-performance wide-temperature-range epoxy resin binder comprises the following components: epoxy resin, modified silicon dioxide, an organic solvent, diethylenetriamine, 1-3 parts of graphene and a silane coupling agent. Oleic acid and cinnamyl alcohol are adopted for the silane coupling agent, and then silicon dioxide is modified through the silane coupling agent, so that the interface adhesive force and compatibility of the silane coupling agent in a system are enhanced. Besides, a flexible siloxy chain segment and a rigid benzene ring structure are also introduced, so that energy can be effectively absorbed when impact force is encountered, and excellent reinforcing and toughening efficiency is shown.

Description

Technical Field

[0001] The invention belongs to the technical field of epoxy resin binders and relates to a high-performance wide-temperature range epoxy resin binder and a preparation method thereof. Background Art

[0002] In the technical scope of steel bridge deck paving, SMA modified asphalt concrete, cast asphalt concrete and epoxy asphalt concrete are currently the most popular materials. In particular, epoxy asphalt materials have become the focus of steel bridge deck paving due to their excellent bonding strength, light weight and outstanding high temperature resistance. Compared with conventional asphalt pavement, epoxy asphalt concrete combines the thermosetting properties of epoxy resin curing material and the thermoplastic properties of matrix asphalt, showing excellent strength, excellent bonding properties and strong corrosion resistance, and has great development potential in the field of road and bridge deck paving. At present, domestic research on high-temperature, high-performance, wide-temperature range epoxy resin binders is still insufficient. The high-performance wide-temperature range epoxy resin binders used by the industry have too fast curing rate, long curing cycle and significant toxicity under high temperature conditions, which has a serious impact on construction. At the same time, the toughness is insufficient, which undoubtedly hinders the widespread application of epoxy resin binders in China. Summary of the invention

[0003] The purpose of the present invention is to provide a high-performance wide-temperature epoxy resin binder and a preparation method thereof. The present invention uses oleic acid and cinnamyl alcohol as silane coupling agents, and then uses them to modify silicon dioxide to enhance its interfacial adhesion and compatibility in the system. In addition, flexible silane alkoxy segments and rigid benzene ring structures are introduced, which can effectively absorb energy when encountering impact force, showing excellent strengthening and toughening performance.

[0004] The purpose of the present invention can be achieved through the following technical solutions:

[0005] A high performance wide temperature range epoxy resin binder comprises the following components:

[0006] Component A is composed of the following components in parts by weight: 30-40 parts of epoxy resin, 20-26 parts of modified silica and 30-40 parts of organic solvent;

[0007] Component B is composed of the following components in parts by weight: 40-60 parts of diethylenetriamine, 1-3 parts of graphene and 1-2 parts of silane coupling agent.

[0008] As a preferred technical solution of the present invention, the epoxy resin is bisphenol A epoxy resin; the silane coupling agent is silane coupling agent KH560; and the organic solvent is one or more of n-butanol, isobutanol and ethyl acetate.

[0009] As a preferred technical solution of the present invention, the preparation method of the modified silicon dioxide comprises the following steps:

[0010] 1) placing silica and anhydrous ethanol in a reaction kettle and stirring them fully, adding a coupling agent, heating and stirring, filtering off the solvent, washing the solid, and vacuum drying to obtain pretreated silica;

[0011] 2) The pretreated silica and anhydrous ethanol are mixed and mechanically stirred, and then a glycine solution is added, heated and mixed, and centrifuged. The solid is taken out for washing and vacuum drying to obtain modified silica.

[0012] As a preferred technical solution of the present invention, in step 1), the sufficient stirring is stirring at a speed of 800-900r / min for 15-20min; the heating and stirring treatment is stirring at a temperature of 63-70°C for 6-8h; the cleaning is cleaning three times with anhydrous ethanol; and the vacuum drying is vacuum drying at a temperature of 80°C to constant weight.

[0013] As a preferred technical solution of the present invention, in step 1), the mass ratio of the silicon dioxide, anhydrous ethanol and coupling agent is 14-16:40-50:3.8-4.2; the coupling agent is a modified coupling agent; and the particle size of the silicon dioxide is 60 nm.

[0014] As a preferred technical solution of the present invention, in step 2), the mechanical stirring and mixing is stirring at a speed of 600-800 r / min for 30-45 min; the heating and mixing is stirring at a temperature of 60-65°C and a speed of 200-300 r / min for 6-8 h; the cleaning is cleaning three times with anhydrous ethanol; and the vacuum drying is vacuum drying at a temperature of 70-80°C to constant weight.

[0015] As a preferred technical solution of the present invention, in step 2), the mass ratio of the pretreated silica, anhydrous ethanol and glycine solution is 10-12:30-36:3.0-3.6; the glycine solution is prepared by mixing glycine, acetic acid and deionized water in a mass ratio of 2.0-2.4:0.10-0.12:25.

[0016] As a preferred technical solution of the present invention, the preparation of the modified coupling agent includes the following steps: diethylenetriaminopropyltrimethoxysilane and anhydrous ethanol are stirred at a speed of 800-900r / min and a temperature of 40-43°C for 32-40min, oleic acid, cinnamyl alcohol and azobisisobutyronitrile are added under stirring at a temperature of 60-65°C and a speed of 520-600r / min for 5-6h, cooled to room temperature, and the solvent is removed by rotary evaporation to obtain the modified coupling agent.

[0017] As a preferred technical solution of the present invention, the mass ratio of diethylenetriaminopropyltrimethoxysilane, anhydrous ethanol, oleic acid, cinnamyl alcohol and azobisisobutyronitrile is 10-12:32-36:7-8:0.6-0.8:0.3-0.4.

[0018] A method for preparing a high-adhesion epoxy anticorrosive binder comprises the following steps:

[0019] S1, mixing the modified silicon dioxide and organic solvent in component A, adding epoxy resin and continuing to stir to obtain a mixture;

[0020] S2. Stir and mix the graphene and silane coupling agent in component B, add diethylenetriamine and continue stirring, and then add the mixture and stir and mix to obtain the product.

[0021] Beneficial effects of the present invention:

[0022] The present invention uses oleic acid and cinnamyl alcohol as silane coupling agents, and then uses them to modify silicon dioxide to enhance its interfacial adhesion and compatibility in the system. In addition, flexible silane alkoxy segments and rigid benzene ring structures are introduced, which can effectively absorb energy when encountering impact force, showing excellent strengthening and toughening performance. DETAILED DESCRIPTION

[0023] In order to further illustrate the technical means and effects adopted by the present invention to achieve the predetermined invention purpose, the specific implementation methods, structures, features and effects of the present invention are described in detail below in combination with the embodiments.

[0024] Example 1

[0025] A high performance wide temperature range epoxy resin binder comprises the following components:

[0026] Component A is composed of the following components in parts by weight: 30 parts of bisphenol A epoxy resin, 20 parts of modified silicon dioxide and 30 parts of n-butanol;

[0027] Component B is composed of the following components in parts by weight: 40 parts of diethylenetriamine, 1 part of graphene and 1 part of silane coupling agent KH560.

[0028] Wherein, the preparation method of the modified silicon dioxide comprises the following steps:

[0029] 1) After placing silicon dioxide and anhydrous ethanol in a reaction kettle and stirring them fully, a coupling agent is added and heated and stirred. After filtering out the solvent, the solid is washed and vacuum dried to obtain pretreated silicon dioxide; the sufficient stirring is stirring at a speed of 800 r / min for 15 minutes; the heating and stirring treatment is stirring at a temperature of 63° C. for 6 hours; the washing is washing with anhydrous ethanol three times; the vacuum drying is vacuum drying at a temperature of 80° C. to constant weight; the mass ratio of silicon dioxide, anhydrous ethanol and coupling agent is 14:40:3.8; the coupling agent is a modified coupling agent; the particle size of silicon dioxide is 60 nm;

[0030] 2) The pretreated silica and anhydrous ethanol are mixed and mechanically stirred, and then a glycine solution is added, heated and mixed, centrifuged, and the solid is washed and vacuum dried to obtain modified silica; the mechanical stirring and mixing is stirring at a speed of 600 r / min for 30 minutes; the heating and mixing is stirring at a temperature of 60°C and a speed of 200 r / min for 6 hours; the washing is washing three times with anhydrous ethanol; the vacuum drying is vacuum drying at a temperature of 70°C to constant weight; the mass ratio of the pretreated silica, anhydrous ethanol and glycine solution is 10:30:3.0; the glycine solution is prepared by mixing glycine, acetic acid and deionized water in a mass ratio of 2.0:0.10:25.

[0031] The preparation of the modified coupling agent includes the following steps: stirring diethylenetriaminopropyltrimethoxysilane and anhydrous ethanol at a speed of 800r / min and a temperature of 40°C for 32min, adding oleic acid, cinnamyl alcohol and azobisisobutyronitrile under stirring, stirring for 5h at a temperature of 60°C and a speed of 520r / min, cooling to room temperature, and removing the solvent by rotary evaporation to obtain the modified coupling agent; the mass ratio of diethylenetriaminopropyltrimethoxysilane, anhydrous ethanol, oleic acid, cinnamyl alcohol and azobisisobutyronitrile is 10:32:7:0.6:0.3.

[0032] A method for preparing a high-adhesion epoxy anticorrosive binder comprises the following steps:

[0033] S1. Stirring and mixing the modified silicon dioxide and n-butanol in component A, adding epoxy resin and continuing to stir to obtain a mixture;

[0034] S2. Stir and mix the graphene in component B and the silane coupling agent KH560, add diethylenetriamine and continue stirring, and then add the mixture and stir and mix to obtain the product.

[0035] Example 2

[0036] A high performance wide temperature range epoxy resin binder comprises the following components:

[0037] Component A is composed of the following components in parts by weight: 35 parts of bisphenol A epoxy resin, 23 parts of modified silicon dioxide and 35 parts of n-butanol;

[0038] Component B is composed of the following components in parts by weight: 50 parts of diethylenetriamine, 2 parts of graphene and 1.5 parts of silane coupling agent KH560.

[0039] Wherein, the preparation method of the modified silicon dioxide comprises the following steps:

[0040] 1) After placing silicon dioxide and anhydrous ethanol in a reaction kettle and stirring them fully, a coupling agent is added and heated and stirred. After filtering out the solvent, the solid is washed and vacuum dried to obtain pretreated silicon dioxide; the sufficient stirring is stirring at a speed of 850r / min for 18min; the heating and stirring treatment is stirring at a temperature of 66°C for 7h; the washing is washing with anhydrous ethanol three times; the vacuum drying is vacuum drying at a temperature of 80°C to constant weight; the mass ratio of silicon dioxide, anhydrous ethanol and coupling agent is 15:45:4; the coupling agent is a modified coupling agent; the particle size of silicon dioxide is 60nm;

[0041] 2) The pretreated silica and anhydrous ethanol are mixed and mechanically stirred, and then a glycine solution is added, heated and mixed, centrifuged, and the solid is washed and vacuum dried to obtain modified silica; the mechanical stirring and mixing is stirring at a speed of 700 r / min for 38 minutes; the heating and mixing is stirring at a temperature of 62°C and a speed of 250 r / min for 7 hours; the washing is washing three times with anhydrous ethanol; the vacuum drying is vacuum drying at a temperature of 75°C to constant weight; the mass ratio of the pretreated silica, anhydrous ethanol and glycine solution is 11:33:3.3; the glycine solution is prepared by mixing glycine, acetic acid and deionized water in a mass ratio of 2.2:0.11:25.

[0042] The preparation of the modified coupling agent includes the following steps: stirring diethylenetriaminopropyltrimethoxysilane and anhydrous ethanol at a speed of 850r / min and a temperature of 42°C for 36min, adding oleic acid, cinnamyl alcohol and azobisisobutyronitrile under stirring, stirring for 5.5h at a temperature of 62°C and a speed of 560r / min, cooling to room temperature, and removing the solvent by rotary evaporation to obtain the modified coupling agent; the mass ratio of diethylenetriaminopropyltrimethoxysilane, anhydrous ethanol, oleic acid, cinnamyl alcohol and azobisisobutyronitrile is 11:34:7.5:0.7:0.35.

[0043] A method for preparing a high-adhesion epoxy anticorrosive binder comprises the following steps:

[0044] S1. Stirring and mixing the modified silicon dioxide and n-butanol in component A, adding epoxy resin and continuing to stir to obtain a mixture;

[0045] S2. Stir and mix the graphene in component B and the silane coupling agent KH560, add diethylenetriamine and continue stirring, and then add the mixture and stir and mix to obtain the product.

[0046] Example 3

[0047] A high performance wide temperature range epoxy resin binder comprises the following components:

[0048] Component A is composed of the following components in parts by weight: 40 parts of bisphenol A epoxy resin, 26 parts of modified silicon dioxide and 40 parts of n-butanol;

[0049] Component B is composed of the following components in parts by weight: 60 parts of diethylenetriamine, 3 parts of graphene and 2 parts of silane coupling agent KH560.

[0050] Wherein, the preparation method of the modified silicon dioxide comprises the following steps:

[0051] 1) After placing silicon dioxide and anhydrous ethanol in a reaction kettle and stirring them fully, a coupling agent is added and heated and stirred. After filtering off the solvent, the solid is washed and vacuum dried to obtain pretreated silicon dioxide; the sufficient stirring is stirring at a speed of 900 r / min for 20 minutes; the heating and stirring treatment is stirring at a temperature of 70° C. for 8 hours; the washing is washing with anhydrous ethanol three times; the vacuum drying is vacuum drying at a temperature of 80° C. to constant weight; the mass ratio of silicon dioxide, anhydrous ethanol and coupling agent is 16:50:4.2; the coupling agent is a modified coupling agent; the particle size of silicon dioxide is 60 nm;

[0052] 2) The pretreated silica and anhydrous ethanol are mixed and mechanically stirred, and then a glycine solution is added, heated and mixed, centrifuged, and the solid is taken for cleaning and vacuum drying to obtain modified silica; the mechanical stirring and mixing is stirring at a speed of 800 r / min for 45 minutes; the heating and mixing is stirring at a temperature of 65°C and a speed of 300 r / min for 8 hours; the cleaning is cleaning three times with anhydrous ethanol; the vacuum drying is vacuum drying at a temperature of 80°C to constant weight; the mass ratio of the pretreated silica, anhydrous ethanol and glycine solution is 12:36:3.6; the glycine solution is prepared by mixing glycine, acetic acid and deionized water in a mass ratio of 2.4:0.12:25.

[0053] The preparation of the modified coupling agent includes the following steps: stirring diethylenetriaminopropyltrimethoxysilane and anhydrous ethanol at a speed of 900 r / min and a temperature of 43°C for 40 minutes, adding oleic acid, cinnamyl alcohol and azobisisobutyronitrile under stirring, stirring at a temperature of 65°C and a speed of 600 r / min for 6 hours, cooling to room temperature, and removing the solvent by rotary evaporation to obtain the modified coupling agent; the mass ratio of diethylenetriaminopropyltrimethoxysilane, anhydrous ethanol, oleic acid, cinnamyl alcohol and azobisisobutyronitrile is 12:36:8:0.8:0.4.

[0054] A method for preparing a high-adhesion epoxy anticorrosive binder comprises the following steps:

[0055] S1. Stirring and mixing the modified silicon dioxide and n-butanol in component A, adding epoxy resin and continuing to stir to obtain a mixture;

[0056] S2. Stir and mix the graphene in component B and the silane coupling agent KH560, add diethylenetriamine and continue stirring, and then add the mixture and stir and mix to obtain the product.

[0057] Comparative Example 1

[0058] Compared with Example 2, Comparative Example 1 is different in that silane coupling agent KH550 is used instead of diethylenetriaminopropyltrimethoxysilane, and the other components, preparation steps and parameters are the same.

[0059] Comparative Example 2

[0060] Compared with Example 2, the difference of Comparative Example 2 is that silane coupling agent KH570 is used instead of diethylenetriaminopropyltrimethoxysilane, and the other components, preparation steps and parameters are the same.

[0061] Comparative Example 3

[0062] Compared with Example 2, Comparative Example 3 is different in that diethylenetriaminopropyltrimethoxysilane is not used, and the other components, preparation steps and parameters are the same.

[0063] Comparative Example 4

[0064] Compared with Example 2, Comparative Example 4 is different in that oleic acid is not used, and the other components, preparation steps and parameters are the same.

[0065] Comparative Example 5

[0066] Compared with Example 2, the difference in Comparative Example 5 is that no coupling agent is used in step 1), and the other components, preparation steps and parameters are the same.

[0067] Comparative Example 6

[0068] Compared with Example 2, the difference in Comparative Example 6 is that glycine is not used in step 2), and the other components, preparation steps and parameters are the same.

[0069] The raw materials of Examples 1-3 and Comparative Examples 1-6 were mixed to obtain a binder, and the samples obtained after curing were tested as follows. The test results are shown in Table 1.

[0070] Mechanical properties test: samples with a size of 20 mm × 10 mm × 0.5 mm were used. A universal testing machine was used with a crosshead speed set at 10 mm / min. Each sample was measured three times (tensile strength and elongation at break), and the average value was calculated as the final result.

[0071] Table 1

[0072]

[0073]

[0074] From the test results in Table 1, it can be seen that compared with Comparative Examples 1-6, the mechanical properties of the binder prepared in Examples 1-3 after curing are significantly better than those in Comparative Examples 1-6.

[0075] From the comparative analysis of Examples 1-3 and Comparative Examples 1-6 in combination with Table 1, it can be seen that the present invention uses oleic acid and cinnamyl alcohol to modify the silane coupling agent and introduce a flexible segment. The modified silane coupling agent promotes the fluidity of silica in the binder composite material and improves its dispersion effect. The hydroxyl groups after silica pretreatment and the carboxyl and amino groups in the glycine solution significantly enhance the grafting efficiency through hydrogen bonds and electrostatic adsorption forces. With the chemical connection between the modified coupling agent and the aldehyde group, more Schiff base structures are obtained, thereby improving stability, giving the material certain self-repairing properties, and strengthening wear resistance and mechanical properties. The hydroxyl groups contained in the modified silica can participate in the reaction in the binder composite material through covalent bonds, while enhancing its interfacial adhesion and compatibility in the system. In addition, flexible silaneoxy segments and rigid benzene ring structures are introduced, which can effectively absorb energy when encountering impact forces, showing superior enhancement and toughening performance.

[0076] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. Although the present invention has been disclosed as a preferred embodiment as above, it is not used to limit the present invention. Any technical personnel in this field can make some changes or modify the technical contents disclosed above into equivalent embodiments without departing from the scope of the technical solution of the present invention. However, any brief modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention are still within the scope of the technical solution of the present invention.

Claims

1. A high-performance wide temperature range epoxy resin binder, characterized in that: Includes the following components: Component A is composed of the following components in parts by weight: 30-40 parts of epoxy resin, 20-26 parts of modified silica and 30-40 parts of organic solvent; Component B is composed of the following components in parts by weight: 40-60 parts of diethylenetriamine, 1-3 parts of graphene and 1-2 parts of silane coupling agent.

2. A high performance wide temperature range epoxy resin binder according to claim 1, characterized in that: The epoxy resin is bisphenol A epoxy resin; the silane coupling agent is silane coupling agent KH560; and the organic solvent is one or more of n-butanol, isobutanol and ethyl acetate.

3. The high-performance wide-temperature range epoxy resin binder according to claim 1, characterized in that: The preparation method of the modified silicon dioxide comprises the following steps: 1) placing silica and anhydrous ethanol in a reaction kettle and stirring them fully, adding a coupling agent, heating and stirring, filtering off the solvent, washing the solid, and vacuum drying to obtain pretreated silica; 2) The pretreated silica and anhydrous ethanol are mixed and mechanically stirred, and then a glycine solution is added, heated and mixed, and centrifuged. The solid is taken out for washing and vacuum drying to obtain modified silica.

4. The high-performance wide-temperature range epoxy resin binder according to claim 1, characterized in that: In step 1), the sufficient stirring is stirring at a speed of 800-900 r / min for 15-20 min; the heating and stirring treatment is stirring at a temperature of 63-70° C. for 6-8 h; the cleaning is cleaning three times with anhydrous ethanol; and the vacuum drying is vacuum drying at a temperature of 80° C. to constant weight.

5. The high-performance wide-temperature range epoxy resin binder according to claim 1, characterized in that: In step 1), the mass ratio of the silicon dioxide, anhydrous ethanol and coupling agent is 14-16:40-50:3.8-4.2; the coupling agent is a modified coupling agent; and the particle size of the silicon dioxide is 60 nm.

6. The high-performance wide-temperature range epoxy resin binder according to claim 1, characterized in that: In step 2), the mechanical stirring and mixing is stirring at a speed of 600-800 r / min for 30-45 min; the heating and mixing is stirring at a temperature of 60-65° C. and a speed of 200-300 r / min for 6-8 h; the cleaning is cleaning three times with anhydrous ethanol; and the vacuum drying is vacuum drying at a temperature of 70-80° C. to constant weight.

7. The high-performance wide-temperature range epoxy resin binder according to claim 1, characterized in that: In step 2), the mass ratio of the pretreated silica, anhydrous ethanol and glycine solution is 10-12:30-36:3.0-3.6; the glycine solution is prepared by mixing glycine, acetic acid and deionized water in a mass ratio of 2.0-2.4:0.10-0.12:

25.

8. The high performance wide temperature range epoxy resin binder according to claim 1, characterized in that: The preparation of the modified coupling agent comprises the following steps: After diethylenetriaminopropyltrimethoxysilane and anhydrous ethanol are stirred at 800-900 r / min and 40-43°C for 32-40 min, oleic acid, cinnamyl alcohol and azobisisobutyronitrile are added under stirring, and stirred at 60-65°C and 520-600 r / min for 5-6 h. After cooling to room temperature, the solvent is evaporated to obtain the product.

9. The high performance wide temperature range epoxy resin binder according to claim 6, characterized in that: The mass ratio of diethylenetriaminopropyltrimethoxysilane, anhydrous ethanol, oleic acid, cinnamyl alcohol and azobisisobutyronitrile is 10-12:32-36:7-8:0.6-0.8:0.3-0.

4.

10. A method for preparing the high-adhesion epoxy anticorrosive binder according to any one of claims 1 to 9, characterized in that: The preparation method of the high-performance wide-temperature range epoxy resin binder comprises the following steps: S1, mixing the modified silicon dioxide and organic solvent in component A, adding epoxy resin and continuing to stir to obtain a mixture; S2. Stir and mix the graphene and silane coupling agent in component B, add diethylenetriamine and continue stirring, and then add the mixture and stir and mix to obtain the product.

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