Formula and preparation method of crack repairing adhesive for concrete containing open water

Abstract

The invention belongs to the technical field of new building materials, and provides a formula and a preparation method of an open water-containing concrete crack repair adhesive, the concrete crack repair adhesive comprises a component A and a component B. The component A comprises epoxy resin, a bifunctional reactive diluent, a monofunctional reactive diluent and a coupling agent; the component B comprises modified mixed amine, modified alicyclic amine and an accelerant, and the modified mixed amine is formed by modifying mixed amine of polyether amine D230 and polyamide 651 through Mannich. The formula of the concrete crack repairing adhesive can be used for an open water-containing concrete interface, and the application range of the crack repairing adhesive is widened; and the use ratio is wide, and the quality risk caused by inaccurate proportioning is greatly reduced.

Description

Technical Field

[0001] The invention belongs to the technical field of new building materials, and more specifically, relates to a formula of concrete crack repair glue containing clear water and a preparation method thereof. Background Art

[0002] Cracking is a common disease of concrete. Harmful environmental media damage concrete and steel bars through cracks, reducing the durability of the structure. In severe cases, it may even threaten the safety of building use. Epoxy resin has good adhesion to concrete, and using it to repair cracks is a common method, but there are also some problems in the application process. Common crack glues on the market are mainly used for dry and wet concrete cracks. Most of them are not suitable for some special use environments, such as concrete cracks containing visible water or seepage. This results in limited choices for construction units, and they have to temporarily use materials such as polyurethane to seal cracks containing visible water. These materials have poor bonding properties and cannot meet the requirements for concrete structure reinforcement, which also adds trouble to subsequent reinforcement measures.

[0003] At the same time, due to reasons such as irregular construction site management, the crack glue is not accurately dispensed. There are even cases where the manufacturer requires the glue to be dispensed by weight, but the construction site uses volume ratio instead, resulting in the AB group ratio exceeding the manufacturer's requirements, which greatly reduces the repair effect.

[0004] In order to solve the above problems, it is urgent to develop a formula of concrete crack repair glue suitable for direct use in concrete containing clear water and a preparation method thereof. Summary of the invention

[0005] One of the purposes of the present invention is to overcome the shortcomings of the above-mentioned prior art and provide a crack repair adhesive formula and a preparation method thereof that can repair concrete cracks containing visible water.

[0006] One aspect of the present invention provides a formula for concrete crack repair glue containing visible water, wherein the concrete crack repair glue comprises component A and component B, wherein the component A comprises: epoxy resin, a bifunctional active diluent, a monofunctional active diluent and a coupling agent; the component B comprises a modified mixed amine, a modified alicyclic amine and an accelerator, wherein the modified mixed amine is a mixed amine of polyetheramine D230 and polyamide 651 modified by Mannich.

[0007] In an embodiment, the monofunctional active diluent may be benzyl glycidyl ether and / or C12-C14 glycidyl ether, the bifunctional active diluent may be 1,4-butanediol glycidyl ether and / or 1,6-hexanediol glycidyl ether, the coupling agent may be γ-(2,3-epoxypropoxy)propyltrimethoxysilane, and the promoter may be 2,4,6-tris(dimethylaminomethyl)phenol.

[0008] In an embodiment, the weight ratio of the components in the A component can be: based on 100 parts of epoxy resin, 8-10 parts of bifunctional active diluent, 8-10 parts of monofunctional active diluent, and 1-3 parts of coupling agent; the weight ratio of the components in the B component can be: 65.2-66.0 parts of modified mixed amine, 32.6-33.0 parts of modified alicyclic amine, and 1.0-2.2 parts of accelerator.

[0009] In an embodiment, the epoxy resin can be E51 and / or NPEL-128 resin, with an epoxy equivalent of 180~200g / eq; the 1,4-butanediol glycidyl ether has an epoxy equivalent of 120~137g / eq; the 1,6-hexanediol glycidyl ether 632 has an epoxy equivalent of 143~154g / eq; the C12-C14 glycidyl ether has an equivalent of 290~310g / eq; the benzyl glycidyl ether has an epoxy equivalent of 210~220g / eq, and the DMP-30 has an amine value of 600~630mgKOH / g.

[0010] In an embodiment, the modified alicyclic amine may be Yexu 6308, having a viscosity of 20-40 mPa·s at 25° C., an amine value of 220-300 mgKOH / g, and an active hydrogen equivalent of 98 g / eq.

[0011] In an embodiment, the Mannich modification may be: using the polyetheramine D230 and the polyamide 651 as core chemical structures, adding paraformaldehyde and phenol, and controlling the reaction conditions to generate the modified mixed amine.

[0012] In an embodiment, the Mannich modification may include the following steps: adding 9.0g-9.8g of phenol per 100g of polyamide 651, heating and stirring, when the temperature reaches 80-90°C, continuing stirring for 30-40min, adding 3.0-3.3g of paraformaldehyde in batches, stirring, and reacting; adding polyetheramine D230, adding 23.0-28.0g of phenol per 100g of polyamide D230, stirring, and adding 7.3-8.9g of paraformaldehyde in batches, stirring, and reacting; and reflux reaction at 100-105°C, and vacuum dehydration to obtain the modified mixed amine.

[0013] Another aspect of the present invention provides a method for preparing a formula of a concrete crack repair adhesive containing visible water, the preparation method comprising: performing Mannich modification on a mixed amine of polyetheramine D230 and polyamide 651 to obtain a modified mixed amine; configuring component A and component B into a formula of a concrete crack repair adhesive containing visible water, wherein the component A comprises: an epoxy resin, a bifunctional active diluent, a monofunctional active diluent and a coupling agent, and the component B comprises the modified mixed amine, a modified alicyclic amine and an accelerator.

[0014] In an embodiment, the Mannich modification may be: using the polyetheramine D230 and the polyamide 651 as core chemical structures, adding paraformaldehyde and phenol, and controlling the reaction conditions to generate the modified mixed amine.

[0015] In an embodiment, the Mannich modification may include the following steps: adding 9.0g-9.8g of phenol per 100g of polyamide 651, heating and stirring, when the temperature reaches 80-90°C, continuing stirring for 30-40min, adding 3.0-3.3g of paraformaldehyde in batches, stirring, and reacting; adding polyetheramine D230, adding 23.0-28.0g of phenol per 100g of polyamide D230, stirring, and adding 7.3-8.9g of paraformaldehyde in batches, stirring, and reacting; and reflux reaction at 100-105°C, and vacuum dehydration to obtain the modified mixed amine.

[0016] Compared with the prior art, the present invention has the following beneficial effects: 1) The epoxy structural adhesive of the present invention can be used for repairing both dry and wet cracks, as well as cracks containing visible water, thus broadening the scope of application of the crack repair adhesive. 2) The crack repair adhesive of the present invention has a wider use ratio, which greatly reduces the quality risk caused by inaccurate ingredients. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] The accompanying drawings illustrate exemplary embodiments of the inventive concept and, together with the description, are used to explain the principles of the inventive concept. The accompanying drawings are included to provide a further understanding of the inventive concept and are incorporated in and constitute a part of this specification. Figure 1 The underwater curing diagram of the steel-concrete bonding specimen made according to Example 1 of the present invention is shown.

[0018] Figure 2 The underwater curing diagram of the steel-concrete bonding specimen prepared according to Comparative Example 2 of the present invention is shown.

[0019] Figure 3 The underwater curing diagram of the steel-concrete bonding specimen prepared according to Comparative Example 3 of the present invention is shown.

[0020] Figure 4 The following is a comparison of the damage effects of crack repair adhesive prepared according to an exemplary embodiment of the present invention on steel-concrete specimens containing water (underwater curing), wherein: Figure 4 Among them, a is comparative example 1, b is comparative example 2, and c is example 1.

[0021] Figure 5 The diagram shows the effect of the crack repair adhesive prepared according to Example 1 of the present invention being applied to the damage form of the water-containing concrete interface bonding specimen.

[0022] Figure 6 The diagram shows the effect of the crack repair adhesive prepared according to Example 2 of the present invention being applied to the damage form of the water-containing concrete interface bonding specimen.

[0023] Figure 7 The diagram shows the effect of the crack repair adhesive prepared according to Example 5 of the present invention being applied to the interface bonding specimen containing water on the failure form.

[0024] Figure 8 The diagram shows the effect of the crack repair adhesive prepared according to Example 6 of the present invention being applied to the interface bonding specimen containing water on the failure form.

[0025] Fig. 9 The diagram shows the effect of the crack repair adhesive prepared according to Example 7 of the present invention being applied to the failure form of a water-containing concrete interface bonding specimen.

[0026] Fig.10 The diagram shows the damage effect of the crack repair adhesive prepared according to comparative example 4 of the present invention applied to a water-containing concrete interface bonding specimen.

[0027] Fig.11 The figure shows the effect of the crack repair adhesive prepared according to comparative example 5 of the present invention being applied to the damage form of the water-containing concrete interface bonding specimen. DETAILED DESCRIPTION

[0028] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0029] Both polyetheramine D230 and polyamide 651 have the advantage of not being strict in curing ratio, but both have certain water solubility and slow curing speed, so they are not suitable for direct use in repairing concrete cracks containing visible water and require targeted modification.

[0030] Based on the above status quo, in order to solve the above problems, the technical concept of the present invention is: to modify the curing agent (D230 and 651 as the main body) with loose glue ratio, to give full play to the performance advantages of different curing agents through ratio design and parameter control, to overcome the negative properties of each component, to give full play to the synergistic effect between materials, and to prepare a crack repair glue formula with a wide ingredient range that can be used for the interface of concrete containing visible water and its preparation method.

[0031] One aspect of the present invention provides a formula for concrete crack repair glue containing visible water, wherein the concrete crack repair glue comprises component A and component B, wherein the component A comprises: epoxy resin, a bifunctional active diluent, a monofunctional active diluent and a coupling agent; the component B comprises a modified mixed amine, a modified alicyclic amine and an accelerator, wherein the modified mixed amine is a mixed amine of polyetheramine D230 and polyamide 651 modified by Mannich.

[0032] The polyetheramine D230 and polyetheramine 651 curing agents have no strict requirements on the use ratio of epoxy resin, so the two are used as the basis for modification. The crack repair adhesive of the present invention has a wider use ratio, which greatly reduces the quality risk caused by inaccurate ingredients. The epoxy structural adhesive of the present invention can be used for repairing dry and wet cracks, as well as cracks containing visible water, which broadens the scope of use of crack repair adhesives. Exemplarily, the monofunctional active diluent may be benzyl glycidyl ether and / or C12-C14 glycidyl ether. The bifunctional active diluent may be 1,4-butanediol glycidyl ether and / or 1,6-hexanediol glycidyl ether. The coupling agent may be γ-(2,3-epoxypropoxy)propyltrimethoxysilane. The promoter may be 2,4,6-tris(dimethylaminomethyl)phenol.

[0033] For example, the weight ratio of each component in component A can be: based on 100 parts of epoxy resin, 8-10 parts of bifunctional active diluent, 8-10 parts of monofunctional active diluent, and 1-3 parts of coupling agent; the weight ratio of each component in component B is: 65.2-66.0 parts of modified mixed amine, 32.6-33.0 parts of modified alicyclic amine, and 1.0-2.2 parts of accelerator.

[0034] Exemplarily, the epoxy resin may be E51 and / or NPEL-128 resin, and the epoxy equivalent may be 180-200 g / eq; 1,4-butanediol glycidyl ether epoxy equivalent is 120-137 g / eq; 1,6-hexanediol glycidyl ether 632 epoxy equivalent is 143-154 g / eq, benzyl glycidyl ether epoxy equivalent is 210-220 g / eq, monofunctional active diluent C12-C14 glycidyl ether equivalent is 290-310 g / eq, and DMP-30 amine value is 600-630 mgKOH / g.

[0035] For example, the modified alicyclic amine may be Yexu 6308, which may have a viscosity of 20-40 mPa·s at 25° C., an amine value of 220-300 mgKOH / g, and an active hydrogen equivalent of 98 g / eq.

[0036] For example, the Mannich modification may be: using polyetheramine D230 and polyamide 651 as core chemical structures, adding paraformaldehyde and phenol, and controlling the reaction conditions to generate the modified mixed amine.

[0037] Exemplarily, the Mannich modification may include the following steps: adding 9.0 g to 9.8 g of phenol per 100 g of polyamide 651, heating and stirring, when the temperature reaches 80 to 90° C., continuing stirring for 30 to 40 min, and then adding 3.0 to 3.3 g of paraformaldehyde in batches, stirring, and reacting; adding polyetheramine D230, adding 23.0 to 28.0 g of phenol per 100 g of polyamide D230, stirring, and adding 7.3 to 8.9 g of paraformaldehyde in batches, stirring, and reacting; reflux reaction at 100 to 105° C., and vacuum dehydration to obtain a modified mixed amine.

[0038] In an exemplary embodiment, the crack repair adhesive is composed of components A and B in a weight ratio of 7:4 to 9:4, wherein the component A is composed of the following weight ratios: 100 parts of epoxy resin, 8 to 10 parts of bifunctional active diluent 1,4-butanediol glycidyl ether (622) or 1,6-hexanediol glycidyl ether (632), 8 to 10 parts of monofunctional active diluent benzyl glycidyl ether (692) or C12-C14 glycidyl ether (AGE), 1 to 3 parts of coupling agent γ-(2,3-epoxypropoxy)propyl trimethoxysilane (KH-560). The component B is composed of 65.2 to 66 parts of modified mixed amine, 32.6 to 33 parts of modified alicyclic amine, and 1 to 2.2 parts of accelerator 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30).

[0039] The epoxy resin is E51 or NPEL-128 resin, with an epoxy equivalent of 180-200 g / eq, the bifunctional active diluents 622 and 632 have epoxy equivalents of 120-137 and 143-154 g / eq, the monofunctional active diluents 692 and AGE have epoxy equivalents of 210-220 and 290-310 g / eq, and the DMP-30 has an amine value of 600-630 mgKOH / g.

[0040] The modified alicyclic amine is Yexu 6308, with a viscosity of 20~40mPa·s (25°C), an amine value of 220~300mgKOH / g, and an active hydrogen equivalent of 98g / eq.

[0041] The modified mixed amine is a mixed amine of polyetheramine D230 and polyamide 651 modified by Mannich. Among them, the active hydrogen equivalent of D230 is 61g / eq, and the amine value of 651 is 380~420mgKOH / g. The D230 and 651 curing agents have no strict requirements on the use ratio of epoxy resin, so the two are used as the basis for modification. The synthetic reaction principle of the mixed amine modified curing agent is as follows:

[0042] in, For polyamide 651; Polyetheramine D230.

[0043] The specific modification methods are as follows: (1) In a 500mL three-necked flask equipped with a reflux condenser, a stirrer and a thermometer, add 100g of polyamide 651, stir evenly, add 9.0-9.8g of phenol, heat and stir, when the temperature rises to 80-90°C, continue stirring for 30-40min, add 3.0-3.3g of paraformaldehyde three times, add evenly each time, stir for 15min after the paraformaldehyde is completely dissolved, add the second time, stir for 15min after the paraformaldehyde is completely dissolved, add the third time, and react for 2h; (2) Add 100g D230 and 23.0-28.0g phenol, stir for 30min, add 7.3-8.9g paraformaldehyde in three times in the same way as (1), and react for 2h.

[0044] (3) Reflux reaction at 100-105°C for 2 hours, and vacuum dehydration at 120°C for 30 minutes to obtain the product.

[0045] Another aspect of the present invention provides a method for preparing a formula of a concrete crack repair adhesive containing visible water, the preparation method comprising: performing Mannich modification on a mixed amine of polyetheramine D230 and polyamide 651 to obtain a modified mixed amine; and configuring component A and component B into a formula of a concrete crack repair adhesive containing visible water, wherein the component A comprises: an epoxy resin, a bifunctional active diluent, a monofunctional active diluent and a coupling agent, and the component B comprises the modified mixed amine, a modified alicyclic amine and an accelerator.

[0046] For example, the Mannich modification may be: using the polyetheramine D230 and the polyamide 651 as core chemical structures, adding paraformaldehyde and phenol, and controlling the reaction conditions to generate the modified mixed amine.

[0047] Exemplarily, the Mannich modification includes the following steps: adding 9.0g to 9.8g of phenol per 100g of polyamide 651, heating and stirring, when the temperature reaches 80°C, continuing stirring, and then adding 3.0 to 3.3g of polyformaldehyde in batches, stirring, and reacting; adding polyetheramine D230, adding 23.0 to 28.0g of phenol per 100g of polyamide D230, stirring, and adding 7.3 to 8.9g of polyformaldehyde in batches, stirring, and reacting; reflux reaction at 100 to 105°C, and vacuum dehydration to obtain the modified mixed amine.

[0048] (4) Exemplarily, the Mannich modification includes the following steps: add 100 g of polyamide 651 to a 500 mL three-necked flask equipped with a reflux condenser, a stirrer and a thermometer, stir evenly, add 9.0-9.8 g of phenol, heat and stir, when the temperature rises to 80°C, continue stirring for 30 min, add 3.0-3.3 g of paraformaldehyde three times, add evenly each time, stir for 15 min after the paraformaldehyde is completely dissolved, add the second time, stir for 15 min after the paraformaldehyde is completely dissolved, add the third time, and react for 2 h; (5) Add 100 g D230 and 23.0-28.0 g phenol, stir for 30 min, add 7.3-8.9 g paraformaldehyde in three times in the same way as (1), and react for 2 h.

[0049] (6) Reflux reaction at 100-105°C for 2 hours, and vacuum dehydration at 120°C for 30 minutes to obtain the product.

[0050] (7) For example, the monofunctional active diluent may be benzyl glycidyl ether and / or C12-C14 glycidyl ether. The bifunctional active diluent may be 1,4-butanediol glycidyl ether and / or 1,6-hexanediol glycidyl ether. The coupling agent may be γ-(2,3-epoxypropoxy)propyltrimethoxysilane. The accelerator may be 2,4,6-tris(dimethylaminomethyl)phenol.

[0051] (8) For example, the weight ratio of each component in component A can be: based on 100 parts of epoxy resin, 8-10 parts of bifunctional reactive diluent, 8-10 parts of monofunctional reactive diluent, and 1-3 parts of coupling agent; the weight ratio of each component in component B can be: 65.2-66.0 parts of modified mixed amine, 32.6-33.0 parts of modified alicyclic amine, and 1.0-2.2 parts of accelerator.

[0052] (9) For example, the epoxy resin may be E51 and / or NPEL-128 resin, and the epoxy equivalent may be 180-200 g / eq; the epoxy equivalent of 1,4-butanediol glycidyl ether is 120-137 g / eq; the epoxy equivalent of 1,6-hexanediol glycidyl ether 632 is 143-154 g / eq; the epoxy equivalent of benzyl glycidyl ether is 210-220 g / eq; the equivalent of monofunctional active diluent C12-C14 glycidyl ether (AGE) is 290-310 g / eq; and the amine value of DMP-30 is 600-630 mgKOH / g.

[0053] (10) For example, the modified alicyclic amine may be Yexu 6308, which has a viscosity of 20-40 mPa·s at 25° C., an amine value of 220-300 mgKOH / g, and an active hydrogen equivalent of 98 g / eq.

[0054] (11) For example, the Mannich modification may be: using polyetheramine D230 and polyamide 651 as the core chemical structure, adding paraformaldehyde and phenol, and controlling the reaction conditions to generate the modified mixed amine.

[0055] (12) For example, the Mannich modification may include the following steps: adding 9.0 g to 9.8 g of phenol per 100 g of polyamide 651, heating and stirring, when the temperature reaches 80 to 90° C., stirring is continued for 30 to 40 min, and then adding 3.0 to 3.3 g of polyformaldehyde in batches, stirring and reacting; adding polyetheramine D230, adding 23.0 to 28.0 g of phenol per 100 g of polyamide D230, stirring, and adding 7.3 to 8.9 g of polyformaldehyde in batches, stirring and reacting; reflux reaction at 100 to 105° C., and vacuum dehydration to obtain a modified mixed amine.

[0056] The technical solution of the present invention is further illustrated below through detailed examples and comparative examples.

[0057] Example 1 Prepare the crack repair adhesive as follows: The crack repair glue is composed of components A and B in a weight ratio of 8:4, wherein the component A is composed of the following weight ratios: 100 parts of E51 epoxy resin, 10 parts of bifunctional active diluent 622, 10 parts of monofunctional active diluent 692, and 1 part of coupling agent KH-560. The component B is composed of 66 parts of modified mixed amine, 33 parts of modified alicyclic amine, and 1 part of accelerator DMP-30.

[0058] The modified alicyclic amine is Yexu 6308, with a viscosity of 20~40mPa·s, an amine value of 220~300mgKOH / g, and an active hydrogen equivalent of 98g / eq.

[0059] Modified mixed amine is a mixture of polyetheramine D230 and polyamide 651 modified by Mannich. The specific modification method is as follows: (1) In a 500mL three-necked flask equipped with a reflux condenser, a stirrer and a thermometer, add 100g of 651, stir evenly, add 9.4g of phenol, heat and stir, when the temperature rises to 80℃, continue stirring for 30min, add 3.0g of paraformaldehyde three times, add 1.0g each time, stir for 15min after the paraformaldehyde is completely dissolved, add the second time, stir for 15min after the paraformaldehyde is completely dissolved, add the third time, and react for 2h; (2) Add 100g D230 and 23.0g phenol, stir for 30min, add 7.3g paraformaldehyde in three times, adding method is the same as step (1), and react for 2h.

[0060] (3) Reflux reaction was carried out at 100-105°C for 2 hours, and vacuum dehydration was carried out at 120°C for 30 minutes to obtain a modified mixed amine. The amine value of the curing agent was tested to be 310 mgKOH / g.

[0061] Example 2 Prepare the crack repair adhesive as follows: The crack repair glue is composed of components A and B in a weight ratio of 8:4, wherein the component A is composed of the following weight ratios: 100 parts of E51 epoxy resin, 8 parts of bifunctional active diluent 622, 8 parts of monofunctional active diluent 692, and 1 part of coupling agent KH-560. The component B is composed of 66 parts of modified mixed amines, 33 parts of modified alicyclic amines, and 1 part of accelerator 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30).

[0062] The modified alicyclic amine is Yexu 6308, with a viscosity of 20~40mPa·s, an amine value of 220~300mgKOH / g, and an active hydrogen equivalent of 98g / eq.

[0063] Modified mixed amine is a mixture of polyetheramine D230 and polyamide 651 modified by Mannich. The specific modification method is as follows: (1) In a 500mL three-necked flask equipped with a reflux condenser, a stirrer and a thermometer, add 100g of 651, stir evenly, add 9.4g of phenol, heat and stir, when the temperature rises to 80℃, continue stirring for 30min, add 3.0g of paraformaldehyde three times, add 1.0g each time, stir for 15min after the paraformaldehyde is completely dissolved, add the second time, stir for 15min after the paraformaldehyde is completely dissolved, add the third time, and react for 2h; (2) Add 100g D230 and 25.5g phenol, stir for 30min, add 8.1g paraformaldehyde in three times, adding method is the same as step (1), and react for 2h.

[0064] (3) Reflux reaction was carried out at 100-105°C for 2 hours, and vacuum dehydration was carried out at 120°C for 30 minutes to obtain a modified mixed amine. The amine value of the curing agent was tested to be 268 mgKOH / g.

[0065] Example 3 Prepare the crack repair adhesive as follows: The crack repair adhesive is prepared from components A and B in a weight ratio of 7:4. The preparation of components A and B is the same as in Example 2.

[0066] Example 4 Prepare the crack repair adhesive as follows: The crack repair adhesive is prepared from components A and B in a weight ratio of 9:4. The preparation of components A and B is the same as in Example 2.

[0067] Example 5 Prepare the crack repair adhesive as follows: The crack repair glue is composed of components A and B in a weight ratio of 8:4, wherein the component A is composed of the following weight ratios: 100 parts of E51 epoxy resin, 9 parts of bifunctional active diluent 622, 9 parts of monofunctional active diluent 692, and 3 parts of coupling agent KH-560. The component B is composed of 66 parts of modified mixed amine, 33 parts of modified alicyclic amine, and 1 part of DMP-30.

[0068] The modified alicyclic amine is Yexu 6308, with a viscosity of 20~40mPa·s, an amine value of 220~300mgKOH / g, and an active hydrogen equivalent of 98g / eq.

[0069] Modified mixed amine is a mixture of polyetheramine D230 and polyamide 651 modified by Mannich. The specific modification method is as follows: (1) In a 500mL three-necked flask equipped with a reflux condenser, a stirrer and a thermometer, add 100g of 651, stir evenly, add 9.4g of phenol, heat and stir, when the temperature rises to 80℃, continue stirring for 30min, add 3.0g of paraformaldehyde three times, add 1.0g each time, stir for 15min after the paraformaldehyde is completely dissolved, add the second time, stir for 15min after the paraformaldehyde is completely dissolved, add the third time, and react for 2h; (2) Add 100g D230 and 28.0g phenol, stir for 30min, add 8.5g paraformaldehyde in three times, adding method is the same as step (1), and react for 2h.

[0070] (3) The mixture was refluxed at 100-105°C for 2 hours and then vacuum-dehydrated at 120°C for 30 minutes to obtain a modified mixed amine. The amine value of the curing agent was tested to be 242 mgKOH / g.

[0071] Example 6 Prepare the crack repair adhesive as follows: The crack repair glue is composed of components A and B in a weight ratio of 8:4, wherein the component A is composed of the following weight ratios: 100 parts of E51 epoxy resin, 10 parts of bifunctional active diluent 632, 10 parts of monofunctional active diluent AGE, and 2 parts of coupling agent KH-560. The component B is composed of 65.2 parts of modified mixed amine, 32.6 parts of modified alicyclic amine, and 2.2 parts of DMP-30.

[0072] The modified alicyclic amine is Yexu 6308, with a viscosity of 20~40mPa·s, an amine value of 220~300mgKOH / g, and an active hydrogen equivalent of 98g / eq.

[0073] Modified mixed amine is a mixture of polyetheramine D230 and polyamide 651 modified by Mannich. The specific modification method is as follows: (1) In a 500mL three-necked flask equipped with a reflux condenser, a stirrer and a thermometer, add 100g of 651, stir evenly, add 9.8g of phenol, heat and stir, when the temperature rises to 80℃, continue stirring for 30min, add 3.3g of paraformaldehyde three times, 1.1g each time, stir for 15min after the paraformaldehyde is completely dissolved, add the second time, stir for 15min after the paraformaldehyde is completely dissolved, add the third time, and react for 2h; (2) Add 100g D230 and 28.0g phenol, stir for 30min, add 8.5g paraformaldehyde in three times, adding method is the same as step (1), and react for 2h.

[0074] (3) The mixture was refluxed at 100-105°C for 2 hours and then vacuum-dehydrated at 120°C for 30 minutes to obtain a modified mixed amine. The amine value of the curing agent was tested to be 249 mgKOH / g.

[0075] Example 7 Prepare the crack repair adhesive as follows: The crack repair glue is composed of components A and B in a weight ratio of 8:4, wherein the component A is composed of the following weight ratios: 100 parts of E51 epoxy resin, 10 parts of bifunctional active diluent 622, 10 parts of monofunctional active diluent 692, and 1 part of coupling agent KH-560. The component B is composed of 66 parts of modified mixed amine, 33 parts of modified alicyclic amine, and 1 part of accelerator DMP-30.

[0076] The modified alicyclic amine is Yexu 6308, with a viscosity of 20~40mPa·s, an amine value of 220~300mgKOH / g, and an active hydrogen equivalent of 98g / eq.

[0077] Modified mixed amine is a mixture of polyetheramine D230 and polyamide 651 modified by Mannich. The specific modification method is as follows: (1) In a 500mL three-necked flask equipped with a reflux condenser, a stirrer and a thermometer, add 100g of 651, stir evenly, add 9.0g of phenol, heat and stir, when the temperature rises to 80℃, continue stirring for 30min, add 3.0g of paraformaldehyde three times, add 1.0g each time, stir for 15min after the paraformaldehyde is completely dissolved, add the second time, stir for 15min after the paraformaldehyde is completely dissolved, add the third time, and react for 2h; (2) Add 100g D230 and 23.0g phenol, stir for 30min, add 7.3g paraformaldehyde in three times, adding method is the same as step (1), and react for 2h.

[0078] (3) Reflux reaction was carried out at 100-105°C for 2 hours, and vacuum dehydration was carried out at 120°C for 30 minutes to obtain a modified mixed amine. The amine value of the curing agent was tested to be 317 mgKOH / g.

[0079] Comparative Example 1 (using only modified mixed amine) Prepare the crack repair adhesive as follows: The crack repair glue is composed of components A and B in a weight ratio of 8:4, wherein the component A is composed of the following weight ratios: 100 parts of E51 epoxy resin, 10 parts of bifunctional active diluent 622, 10 parts of monofunctional active diluent 692, and 1 part of coupling agent KH-560. The component B is a modified mixed amine, and the modification process is the same as in Example 1.

[0080] Comparative Example 2 (without adding modified mixed amine) Prepare the crack repair adhesive as follows: The crack repair glue is composed of components A and B in a weight ratio of 8:4, wherein the component A is composed of the following weight ratios: 100 parts of E51 epoxy resin, 10 parts of bifunctional active diluent 622, 10 parts of monofunctional active diluent 692, and 1 part of coupling agent KH-560. The component B is modified alicyclic amine 6308.

[0081] Comparative Example 3 (unmodified) Prepare the crack repair adhesive as follows: The crack repair glue is composed of components A and B in a weight ratio of 10:4, wherein the component A is composed of the following weight ratios: 100 parts of E51 epoxy resin, 10 parts of bifunctional active diluent 622, 10 parts of monofunctional active diluent 692, and 1 part of coupling agent KH-560. The component B is composed of 33 parts of D230, 33 parts of 651 modified mixed amine, 33 parts of modified alicyclic amine, and 1 part of accelerator DMP-30.

[0082] The modified alicyclic amine is Yexu 6308, with a viscosity of 20~40mPa·s, an amine value of 220~300mgKOH / g, and an active hydrogen equivalent of 98g / eq.

[0083] Comparative Example 4 (too little phenol and formaldehyde) Prepare the crack repair adhesive as follows: The crack repair glue is composed of components A and B in a weight ratio of 8:4, wherein the component A is composed of the following weight ratios: 100 parts of E51 epoxy resin, 10 parts of bifunctional active diluent 622, 10 parts of monofunctional active diluent 692, and 1 part of coupling agent KH-560. The component B is composed of 66 parts of modified mixed amine, 33 parts of modified alicyclic amine, and 1 part of accelerator DMP-30.

[0084] The modified alicyclic amine is Yexu 6308, with a viscosity of 20~40mPa·s, an amine value of 220~300mgKOH / g, and an active hydrogen equivalent of 98g / eq.

[0085] Modified mixed amine is a mixture of polyetheramine D230 and polyamide 651 modified by Mannich. The specific modification method is as follows: (1) In a 500mL three-necked flask equipped with a reflux condenser, a stirrer and a thermometer, add 100g of 651, stir evenly, add 9.0g of phenol, heat and stir, when the temperature rises to 80℃, continue stirring for 30min, add 3.0g of paraformaldehyde three times, add 1.0g each time, stir for 15min after the paraformaldehyde is completely dissolved, add the second time, stir for 15min after the paraformaldehyde is completely dissolved, add the third time, and react for 2h; (2) Add 100g D230 and 18.0g phenol, stir for 30min, add 5.7g paraformaldehyde in three times in the same way as (1), and react for 2h.

[0086] (3) Reflux reaction at 100-105°C for 2 hours, and then vacuum dehydration at 120°C for 30 minutes to obtain the product.

[0087] Comparative Example 5 (Excessive amount of phenol and formaldehyde) Prepare the crack repair adhesive as follows: The crack repair glue is composed of components A and B in a weight ratio of 8:4, wherein the component A is composed of the following weight ratios: 100 parts of E51 epoxy resin, 10 parts of bifunctional active diluent 622, 10 parts of monofunctional active diluent 692, and 1 part of coupling agent KH-560. The component B is composed of 66 parts of modified mixed amine, 33 parts of modified alicyclic amine, and 1 part of accelerator DMP-30.

[0088] The modified alicyclic amine is Yexu 6308, with a viscosity of 20~40mPa·s, an amine value of 220~300mgKOH / g, and an active hydrogen equivalent of 98g / eq.

[0089] Modified mixed amine is a mixture of polyetheramine D230 and polyamide 651 modified by Mannich. D230 and 651 curing agents have no strict requirements on the ratio of epoxy resin, so they are used as the basis for modification. The specific modification method is as follows: (1) In a 500mL three-necked flask equipped with a reflux condenser, a stirrer and a thermometer, add 100g of 651, stir evenly, add 9.8g of phenol, heat and stir, when the temperature rises to 80℃, continue stirring for 30min, add 3.3g of paraformaldehyde three times, 1.1g each time, stir for 15min after the paraformaldehyde is completely dissolved, add the second time, stir for 15min after the paraformaldehyde is completely dissolved, add the third time, and react for 2h; (2) Add 100g D230 and 33.0g phenol, stir for 30min, add 10.5g paraformaldehyde in three times, adding method is the same as step (1), and react for 2h.

[0090] (3) Reflux reaction at 100-105°C for 2 hours, and then vacuum dehydration at 120°C for 30 minutes to obtain the product.

[0091] Test Case Performance test: Take the C45 concrete test block out of the water and shake off some of the visible water without wiping it. Apply glue to the surface of the test block and bond a 40*40 steel block. Immediately put it into underwater curing for 7 days to test the bonding performance of the water-containing concrete interface. The steel-to-steel tensile shear strength, steel-to-steel butt tensile strength and steel-to-wet concrete bonding strength are tested in accordance with GB50728-2011. The bonding performance is shown in Table 1.

[0092] Table 1. Performance test results of examples and comparative examples

[0093] From the comparison of crack glue performance in Table 1, it can be seen that the crack glue using only modified mixed amine (Comparative Example 1) has bonding performance that meets the requirements of GB50728-2011, but does not have underwater bonding ability.

[0094] Modified alicyclic amine 6308 cannot be used alone (Comparative Example 2). Although 6308 is insoluble in water and only the edge of the colloid turns slightly white under water, it has poor wetting effect on the interface of water-containing concrete (see Figure 2 ), resulting in poor bonding performance and too low tensile shear strength to be used alone.

[0095] The "mixed amine + modified alicyclic amine" has insufficient bonding performance on the water-containing concrete interface (Comparative Example 3). Since both D230 and 651 are water-soluble and have good wetting effects, the colloid is almost flat on the water-containing concrete substrate (see Figure 3 ), but the colloid and water may mix, resulting in insufficient bonding performance on the interface of water-containing concrete.

[0096] Compared with Comparative Example 2, Example 1 forms a modified mixed amine by Mannich reaction with D230 and 651, and then cold mixes it with modified alicyclic amine. The water solubility of the prepared "mixed amine Mannich base + modified alicyclic amine" crack glue is greatly reduced, the whitening condition is improved, and it can also be spread on the concrete interface (see Figure 1 ), the bonding strength is 2.4MPa, and cohesive failure of concrete occurs during the test.

[0097] The use of "Mixed amine Mannich base + modified alicyclic amine" curing agent first improves the bonding performance of the crack glue at the interface of water-containing concrete, and secondly achieves the unification of the toughness and rigidity of the crack glue. The "Mixed amine Mannich base + modified alicyclic amine" solution not only solves the problem of high brittleness of the crack glue of single modified alicyclic amine (Comparative Example 2), and the elongation at break is increased from 1.1% to 3.9%, but also overcomes the defect of insufficient rigidity of "mixed amine + modified alicyclic amine" (Comparative Example 3), and increases the butt tensile strength from 19.0MPa to 24.1MPa, balancing the rigidity and toughness of the crack glue.

[0098] From the above analysis, it is very necessary to perform Mannich modification on the D230 and 651 mixed amines. However, the use of modified mixed amines alone cannot meet the requirements for bonding at water-containing interfaces. This can also be seen from the form of bonding failure at the interface of concrete containing visible water. Figure 4 It can be seen that when only the modified mixed amine (Comparative Example 1) and the unmodified crack glue (Comparative Example 2) are used, the bonding specimens are interface failures, and the bonding ability of the colloid to water concrete is weak. After modification (Example 1), the bonding specimens are obviously concrete cohesive failures, and the bonding to water concrete is significantly enhanced.

[0099] The amount of phenol and formaldehyde in the Mannich reaction directly affects the bonding performance of the crack glue to the interface of water-containing concrete. It can be seen from Table 2 that when the amount of phenol formaldehyde is insufficient (Comparative Example 4), the crack glue has a certain bonding ability to the interface of water-containing concrete, and the specimen is mixed and damaged, and the entire interface is not completely bonded (see Fig.10 ), and the rigidity is also slightly low, the butt tensile strength is only 21.9MPa, and the surplus value is not high. When the amount of phenolic formaldehyde is too much, the crack glue is too hydrophobic, and the infiltration of the water-containing concrete interface is poor, resulting in almost interface failure when the specimen is damaged (see Fig.11 ), the toughness of the crack glue is also insufficient, with an elongation at break of 1.9% and a tensile shear strength of only 14.6MPa.

[0100] The dosage of phenolic formaldehyde in Examples 1, 2, 5, 6 and 7 is appropriate, and the requirements for the bonding ability of water-containing concrete, tensile shear strength, butt tensile strength and elongation at break are all met.

[0101] Table 2 Performance test results of examples and comparative examples serial number Tensile shear strength Butt tensile strength Wet concrete bond strength Water-containing concrete interface bonding strength Elongation at break Require ≧15MPa ≧20MPa ≧1.8MPa, concrete cohesive failure / ≧1.7% Example 1 18.1 24.1 2.9 Cohesive failure of concrete 2.4 Concrete cohesive failure 4.2 Example 2 16.5 28.1 3.2 Concrete cohesive failure 2.5 Concrete cohesive failure 4.6 Example 5 17.0 25.8 3.1 Concrete cohesive failure 2.2MPa concrete cohesive failure 3.2 Example 6 16.3 27.8 3.0 Concrete cohesive failure 2.4MPa concrete cohesive failure 2.7 Example 7 16.8 26.2 2.9 Cohesive failure of concrete 2.3MPa concrete cohesive failure 2.5 Comparative Example 4 17.9 21.9 2.3 Concrete cohesive failure Interface damage 6.7 Comparative Example 5 14.6 32.5 2.5 Concrete cohesive failure Interface damage 1.9 The ratio range of the crack glue AB components was also investigated, and the results are shown in Table 3. The ratio of A and B components was set to 7:4 (Example 3), 8:4 (Example 2) and 9:4 (Example 4). The theoretical ratio of A and B components was 8:4, and the use ratio was adjusted up and down by 12.5%. The performance of the crack glue did not change substantially, and all indicators met the requirements of GB50728-2011, indicating that the ratio of the crack glue of the present invention is not strict, and the construction site can make a certain range of adjustments according to the construction process requirements such as mixing viscosity and operable time.

[0102] Table 3 Effect of different usage ratios on crack glue performance

[0103] In summary, the crack repair adhesive prepared by the "mixed amine Mannich base + modified alicyclic amine" curing agent scheme adopted in the present invention not only meets the performance requirements of GB50728-2011, but also gives the product excellent bonding ability on the interface of water-containing concrete. At the same time, it has a wide range of use ratios and can achieve effective bonding on the interfaces of dry, wet and water-containing concrete, helping to solve many difficult and painful problems on the construction site from a material perspective.

Claims

1. A formula for concrete crack repair glue containing clear water, characterized in that: The concrete crack repair glue comprises component A and component B, wherein: The component A comprises: epoxy resin, bifunctional active diluent, monofunctional active diluent and coupling agent; The B component includes a modified mixed amine, a modified alicyclic amine and an accelerator, wherein the modified mixed amine is a mixed amine of polyetheramine D230 and polyamide 651 modified by Mannich.

2. The formula of concrete crack repair glue containing clear water according to claim 1, characterized in that: The monofunctional active diluent is benzyl glycidyl ether and / or C12-C14 glycidyl ether, the bifunctional active diluent is 1,4-butanediol glycidyl ether and / or 1,6-hexanediol glycidyl ether, the coupling agent is γ-(2,3-epoxypropoxy)propyltrimethoxysilane, and the accelerator is 2,4,6-tris(dimethylaminomethyl)phenol.

3. The formula of concrete crack repair glue containing clear water according to claim 2, characterized in that: The weight ratio of the components in the A component is: based on 100 parts of epoxy resin, 8-10 parts of bifunctional active diluent, 8-10 parts of monofunctional active diluent, and 1-3 parts of coupling agent; The weight ratio of the components in the B component is: 65.2-66.0 parts of modified mixed amine, 32.6-33.0 parts of modified alicyclic amine, and 1.0-2.2 parts of accelerator.

4. The formula of concrete crack repair glue containing clear water according to claim 2, characterized in that: The epoxy resin is E51 and / or NPEL-128 resin, and the epoxy equivalent is 180-200 g / eq; the epoxy equivalent of the 1,4-butanediol glycidyl ether is 120-137 g / eq; the epoxy equivalent of the 1,6-hexanediol glycidyl ether 632 is 143-154 g / eq; the equivalent of the C12-C14 glycidyl ether is 290-310 g / eq; the epoxy equivalent of the benzyl glycidyl ether is 210-220 g / eq, and the amine value of the DMP-30 is 600-630 mgKOH / g.

5. The formula of concrete crack repair glue containing clear water according to claim 1, characterized in that: The modified alicyclic amine is Yexu 6308, which has a viscosity of 20-40 mPa·s at 25° C., an amine value of 220-300 mgKOH / g, and an active hydrogen equivalent of 98 g / eq.

6. The formula of concrete crack repair glue containing clear water according to claim 1, characterized in that: The Mannich modification is: using the polyetheramine D230 and the polyamide 651 as the core chemical structure, adding paraformaldehyde and phenol, and controlling the reaction conditions to generate the modified mixed amine.

7. The formula of concrete crack repair glue containing clear water according to claim 1, characterized in that: The Mannich modification comprises the following steps: Add 9.0g~9.8g phenol per 100g polyamide 651, stir while heating, when the temperature rises to 80~90℃, continue stirring for 30~40min, then add 3.0~3.3g paraformaldehyde in batches, stir and react; Add polyetheramine D230, based on 100g of polyamide D230, add 23.0-28.0g of phenol, stir, and add 7.3-8.9g of paraformaldehyde in batches, stir, and react; and The modified mixed amine is obtained by reflux reaction at 100-105°C and vacuum dehydration.

8. A method for preparing a concrete crack repair adhesive formulation containing clear water, characterized in that: The preparation method comprises: Mannich modification is performed on a mixed amine of polyetheramine D230 and polyamide 651 to obtain a modified mixed amine; Component A and component B are configured into a formula for concrete crack repair glue containing visible water, wherein the component A includes: epoxy resin, bifunctional active diluent, monofunctional active diluent and coupling agent, and the component B includes the modified mixed amine, modified alicyclic amine and accelerator.

9. The method for preparing a concrete crack repair adhesive formulation containing clear water according to claim 8, characterized in that: The Mannich modification is: using the polyetheramine D230 and the polyamide 651 as the core chemical structure, adding paraformaldehyde and phenol, and controlling the reaction conditions to generate the modified mixed amine.

10. The method for preparing a concrete crack repair adhesive formulation containing clear water according to claim 8, characterized in that: The Mannich modification comprises the following steps: Add 9.0g~9.8g phenol per 100g polyamide 651, stir while heating, when the temperature rises to 80~90℃, continue stirring for 30~40min, then add 3.0~3.3g paraformaldehyde in batches, stir and react; Add polyetheramine D230, based on 100g of polyamide D230, add 23.0-28.0g of phenol, stir, and add 7.3-8.9g of paraformaldehyde in batches, stir, and react; and The modified mixed amine is obtained by reflux reaction at 100-105°C and vacuum dehydration.

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