A low-temperature and highly active epoxy splicing adhesive and its application

Abstract

The present invention relates to the technical field of splicing adhesives, and specifically discloses a low-temperature and high-activity epoxy splicing adhesive and its application. The epoxy splicing adhesive comprises the following raw materials: epoxy resin, amine curing agent, vinyl resin, transition metal ion salt solution, tertiary amine accelerator and organic peroxide. By limiting the raw material components, a special double-initiated promotion system is constructed. The nitrogen atom in the tertiary amine accelerator acts as a ligand, which can be combined with the transition metal ions in the transition metal ion salt solution at low temperature to form a stable complex through coordination. The complex can activate the organic peroxide at an extremely low temperature, and by accepting or giving electrons, the energy barrier of the decomposition of the organic peroxide is reduced, so that the organic peroxide generates free radicals, thereby initiating the self-polymerization reaction of the vinyl resin, generating a large amount of reaction heat, and promoting the curing reaction of the epoxy resin and the amine curing agent, which has good market application value.

Description

Technical Field

[0001] The invention relates to the technical field of splicing adhesives, and in particular to a low-temperature and high-activity epoxy splicing adhesive and applications thereof. Background Art

[0002] The unit capacity of low-altitude wind turbines is only about 2.5MW, and the power generation efficiency is low. In order to improve the power generation efficiency, the wind turbines are beginning to develop in a large-scale manner. The increase in the power generation of a single unit requires a larger rotor diameter to increase the wind swept area, and also requires a higher tower height as support. At present, the wind turbine tower adopts a segmented prefabricated segment splicing design. As a production method of industrial modular construction, this technology can realize factory-based, standardized and rapid production of products. The materials that play a role in bonding, waterproofing and sealing in the prefabricated segment splicing technology mainly include different types of high-performance adhesives, such as polyurethane sealants, silicone sealants, modified asphalt sealing materials, acrylic sealants and epoxy resin adhesives. Among them, the modified epoxy resin adhesive has high early compressive strength, wet heat aging ability and long-term stress resistance, so it can provide high and long-term bonding strength, which is very suitable for the splicing construction of wind power mixed towers.

[0003] The curing process of epoxy resin is usually a cross-linking reaction between epoxy groups and curing agents (such as amines, anhydrides, etc.). This reaction is exothermic and its rate is significantly affected by temperature. Generally, the rate of chemical reaction increases with increasing temperature. When the temperature rises, the average kinetic energy of the molecules increases, and more molecules can reach the activation energy required for the reaction, thereby accelerating the reaction rate; conversely, at low temperatures, the energy of the molecules is lower, and the number of molecules that reach the activation energy of the reaction decreases, resulting in a slower reaction rate. In addition, the activity of many curing agents decreases at low temperatures, and the reaction efficiency with epoxy groups decreases accordingly. For example, amine curing agents may become viscous or even solidify at low temperatures, making it difficult to fully mix and react with epoxy resins. At present, modified epoxy resin adhesives generally require to be used in an environment above 5°C to cure normally. They cure slowly or even not cure at all in low temperature and severe cold environments. my country's wind resources are mainly concentrated in the northern region, and the temperature is below 0°C or even below -20°C for almost half of the year. Modified epoxy resin adhesives cannot cure normally in severe cold environments, so their strength cannot meet the standard requirements, which seriously restricts the large-scale construction and application of wind power towers. Summary of the invention

[0004] In view of the above problems, the present invention provides a low-temperature and high-activity epoxy splicing adhesive and a preparation method and application thereof. By limiting the raw material components, a special double-initiated promotion system is constructed, which can realize the free radical polymerization reaction of vinyl resin at extremely low temperatures (-15°C ~ -5°C), thereby increasing the temperature of the adhesive layer of the entire epoxy splicing adhesive, thereby promoting the curing reaction of the epoxy splicing adhesive to achieve the specified strength and excellent construction performance.

[0005] In order to achieve the above-mentioned object of the invention, the present invention adopts the following technical solutions: In a first aspect, the present invention provides a low-temperature and high-activity epoxy splicing adhesive, comprising the following raw materials: epoxy resin, amine curing agent, vinyl resin, transition metal ion salt solution, tertiary amine accelerator and organic peroxide.

[0006] Compared with the prior art, the low-temperature and high-activity epoxy splicing adhesive (epoxy splicing adhesive for short) provided by the present invention has constructed a special double-initiated promotion system by limiting the raw material components. After the raw materials are mixed, the nitrogen atoms in the tertiary amine accelerator can be used as ligands to combine with the transition metal ions in the transition metal ion salt solution at low temperature to form a stable complex through coordination. Further, the formed complex can activate organic peroxides at extremely low temperatures, and by accepting or giving electrons, the energy barrier for the decomposition of organic peroxides is reduced, so that the organic peroxides generate free radicals, which in turn trigger the self-polymerization reaction of the vinyl resin, generate a large amount of reaction heat, and promote the curing reaction of the epoxy resin and the amine curing agent. The first initiation of the present invention realizes the decomposition of the organic peroxide at an extremely low temperature by means of the coordination effect of the transition metal ions and the tertiary amines; the second initiation triggers the free radical polymerization of the vinyl resin through the free radicals generated by the decomposition of the organic peroxide, thereby generating sufficient heat to promote the curing reaction of the epoxy splicing adhesive.

[0007] The present invention adopts a special double-initiated promotion system, and uses the vinyl resin self-polymerization reaction system as the built-in heat source of the entire epoxy resin-amine curing agent system, thereby achieving effective control of the curing reaction temperature and having high market application value. Compared with the existing external electric heating, the low-temperature and high-activity epoxy splicing adhesive provided by the present invention reduces power consumption, has more precise temperature control, and has better sealing and bonding effects; compared with the existing use of thiourea to modify amine curing agents, the low-temperature and high-activity epoxy splicing adhesive provided by the present invention will not increase the brittleness of the epoxy splicing adhesive, thereby ensuring the impact resistance and crack resistance of the epoxy splicing adhesive, while avoiding the sulfur atoms participating in the curing reaction and causing the cured product to be degraded.

[0008] Preferably, the epoxy resin includes amino multifunctional epoxy resin and bisphenol F epoxy resin.

[0009] The present invention adopts amino multifunctional epoxy resin, bisphenol F epoxy resin and vinyl resin for compounding, which can further solve the problem that the epoxy resin has high viscosity and is easy to crystallize under low temperature environment.

[0010] Preferably, the amine curing agent includes a modified fatty amine curing agent and a modified alicyclic amine curing agent.

[0011] The present invention adopts a curing agent compounded with a modified fatty amine curing agent and a modified alicyclic amine curing agent, further solving the problem that the amine curing agent has high viscosity and difficult construction under low temperature environment. The modified fatty amine curing agent makes the epoxy splicing adhesive have higher strength in the early stage, and the modified alicyclic amine curing agent ensures that the entire epoxy splicing adhesive system has a longer application period, prolongs the bonding time of the epoxy splicing adhesive, and meets the time requirements of actual on-site assembly.

[0012] Preferably, the low temperature and high activity epoxy splicing adhesive comprises component A, component B and component C; wherein, The component A comprises amino multifunctional epoxy resin, bisphenol F epoxy resin, vinyl resin, transition metal ion salt solution, active diluent, silane coupling agent, thixotropic agent, silicon powder and quartz sand in a mass ratio of (25-50):(5-10):(15-30):(2-6):(5-10):(2-8):(2-10):(80-120):(100-150); The B component includes a modified fatty amine curing agent, a tertiary amine accelerator, a thixotropic agent and silica powder in a mass ratio of (10-20):(2-8):(2-5):(40-80); The C component includes a modified alicyclic amine curing agent and an organic peroxide in a mass ratio of (10-20):(3-10).

[0013] The present invention limits the raw materials and proportions of component A, component B and component C, thereby further strengthening the initiation-promoting effect of each raw material in the dual initiation system, controlling the heat generated during the free radical polymerization of the vinyl resin, and further controlling the curing reaction of the epoxy splicing adhesive, improving the sealing and bonding effects, and achieving the target mechanical strength and durability; it can also ensure that component A and component B are in a paste state and component C is in a liquid state, thereby ensuring that each component has better construction performance at low temperatures.

[0014] Further preferably, the mass ratio of the component A, the component B and the component C is (1.5-2.5):1:(0.4-1.2).

[0015] The invention can further ensure the high activity of the epoxy splicing adhesive by controlling the addition amount of each component, thereby improving the construction performance, mechanical properties and durability of the epoxy splicing adhesive after curing.

[0016] For example, the amino multifunctional epoxy resin may be an amino trifunctional epoxy resin or an amino tetrafunctional epoxy resin. For example, the amino multifunctional epoxy resin includes at least one of AFG-90, AG-70, or AFG-90MH.

[0017] For example, the bisphenol F epoxy resin includes REF-170.

[0018] Preferably, the vinyl resin comprises bisphenol A type epoxy vinyl resin.

[0019] Exemplary vinyl resins include Ashland 411 bisphenol A epoxy vinyl resin.

[0020] Preferably, the transition metal ion salt in the transition metal ion salt solution includes at least one of chlorides or sulfates corresponding to cobalt, iron, copper, manganese or nickel.

[0021] Further preferably, the transition metal ion salt includes at least one of CoCl2, FeSO4, FeCl3, FeCl2, CuSO4, CuCl2, MnSO4, MnCl2, NiSO4 or NiCl2.

[0022] Preferably, the solvent of the transition metal ion salt solution includes at least one of methanol, ethanol or glycerol.

[0023] In the present invention, the transition metal ion salt is used as a raw material in the form of a solution, and the organic solvent can effectively improve the solubility characteristics of the transition metal ion salt in the epoxy resin and better exert the coordination effect of the transition metal ion salt and the tertiary amine in the tertiary amine accelerator.

[0024] Preferably, the concentration of the transition metal ion salt solution is 20wt%~50wt%.

[0025] For example, a transition metal ion salt is added to a solvent at 40° C. to 60° C. and mixed evenly to obtain a transition metal ion salt solution.

[0026] Further preferably, the active diluent includes a glycidyl ether active diluent.

[0027] More preferably, the reactive diluent includes at least one of tert-butylphenyl glycidyl ether, octyl glycidyl ether, resorcinol diglycidyl ether or triethylene glycol diglycidyl ether.

[0028] More preferably, the silane coupling agent includes an epoxy silane coupling agent.

[0029] Exemplary silane coupling agents include glycidoxypropyltrimethoxysilane.

[0030] Further preferably, the thixotropic agent includes at least one of fumed silica, organic bentonite or polyamide wax.

[0031] More preferably, the thixotropic agent is fumed silica.

[0032] More preferably, the particle size of the silicon micropowder is 400 mesh to 600 mesh.

[0033] Further preferably, the particle size of the quartz sand is 40 mesh to 100 mesh.

[0034] In the present invention, the silicon micropowder and quartz sand can be graded, for example, quartz sands of 40-80 mesh, 80-120 mesh and 100-200 mesh can be selected for grading.

[0035] Further preferably, the modified fatty amine curing agent includes triethylenetetramine.

[0036] Preferably, the tertiary amine accelerator includes at least one of 2,4,6-tris(dimethylaminomethyl)phenol, N,N-dimethylaniline or N,N-diethylaniline.

[0037] More preferably, the modified alicyclic amine curing agent includes 1,3-bis(aminomethyl)cyclohexane (1,3-BAC).

[0038] Preferably, the organic peroxide includes one of methyl ethyl ketone peroxide, cyclohexanone peroxide, benzoyl peroxide or 2,4-dichlorobenzoyl peroxide.

[0039] The present invention can further bring into play the synergistic effect of the raw materials by limiting the specific components of the raw materials, thereby further improving the comprehensive performance of the epoxy splicing adhesive.

[0040] In a second aspect, the present invention provides a method for preparing the low-temperature and high-activity epoxy splicing adhesive, comprising the following steps: S1, weighing the raw materials of component A according to the designed ratio, mixing amino multifunctional epoxy resin, bisphenol F type epoxy resin, vinyl resin, transition metal ion salt solution, active diluent and silane coupling agent, and then adding thixotropic agent, silicon micropowder and quartz sand to obtain component A; S2, weighing the raw materials of component B according to the designed ratio, mixing the modified fatty amine curing agent, the tertiary amine accelerator and the silicon powder, and then adding the thixotropic agent to obtain component B; S3, weighing the raw materials of component C according to the designed ratio, mixing the modified alicyclic amine curing agent and the organic peroxide to obtain component C.

[0041] The preparation method of the low-temperature high-activity epoxy splicing adhesive provided by the present invention is simple to operate. It should be noted that there is no limit to the order of S1 to S3. When used, component A, component B and component C are mixed evenly.

[0042] In a third aspect, the present invention provides an application of the low-temperature and high-activity epoxy splicing adhesive in the reinforcement of a wind power hybrid tower structure. DETAILED DESCRIPTION

[0043] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0044] Example 1 This embodiment provides a low-temperature, high-activity epoxy splicing adhesive, which is composed of component A, component B, and component C in a mass ratio of 2:1:1. Component A is composed of the following raw materials: amino multifunctional epoxy resin (AFG-90) with a mass ratio of 40:8:25:4:7:5:8:100:120, bisphenol F epoxy resin (REF-170), vinyl resin (Ashland 411 bisphenol A epoxy vinyl resin), transition metal ion salt solution (methanol solution containing 30wt% CoCl2 and 40wt% NiCl2), active diluent (tert-butylphenyl glycidyl ether), silane coupling agent (glycidoxypropyltrimethoxysilane), thixotropic agent (fumed silica), silicon micropowder with a grade of 400 mesh to 600 mesh, and quartz sand with a grade of 40 mesh to 80 mesh, 80 mesh to 120 mesh, and 100 mesh to 200 mesh.

[0045] Component B is composed of the following raw materials: a modified fatty amine curing agent (triethylenetetramine) in a mass ratio of 15:6:60:4, a tertiary amine accelerator (2,4,6-tris(dimethylaminomethyl)phenol), a thixotropic agent (fumed silica) and silicon micropowder with a gradation of 400 mesh to 600 mesh.

[0046] Component C is composed of the following raw materials: a modified alicyclic amine curing agent (1,3-BAC) and an organic peroxide (methyl ethyl ketone peroxide) in a mass ratio of 12:6.

[0047] The preparation method of the above-mentioned low-temperature high-activity epoxy splicing adhesive comprises the following steps: S1, weigh the raw materials of component A according to the designed ratio, add CoCl2 and NiCl2 into methanol at 50°C, mix well, and obtain a transition metal ion salt solution; The amino multifunctional epoxy resin, bisphenol F epoxy resin, vinyl resin, transition metal ion salt solution, active diluent and silane coupling agent are mixed, and then a thixotropic agent, silicon micropowder and quartz sand are added and mixed evenly to obtain component A.

[0048] S2, weighing the raw materials of component B according to the designed ratio, mixing the modified fatty amine curing agent, the tertiary amine accelerator and the silicon powder, and then adding the thixotropic agent, mixing evenly, to obtain component B.

[0049] S3, weighing the raw materials of component C according to the designed ratio, mixing the modified alicyclic amine curing agent and the organic peroxide to obtain component C.

[0050] There is no restriction on the order between S1~S3.

[0051] S4. Weigh each component according to the designed ratio. Before use, premix component A with component B, then add component C and mix evenly to obtain low-temperature and high-activity epoxy splicing adhesive.

[0052] Example 2 This embodiment provides a low-temperature, high-activity epoxy splicing adhesive, which is composed of component A, component B, and component C in a mass ratio of 1.8:1:0.8. Component A is composed of the following raw materials: amino multifunctional epoxy resin (AG-70) with a mass ratio of 45:5:20:4:8:4:6:110:110, bisphenol F epoxy resin (REF-170), vinyl resin (Ashland 411 bisphenol A epoxy vinyl resin), transition metal ion salt solution (ethanol solution containing 40wt% FeSO4 and 30wt% CuSO4), active diluent (octyl glycidyl ether), silane coupling agent (glycidyl trimethoxy silane), thixotropic agent (equal mass of organic bentonite and polyamide wax), silicon micropowder with a grade of 400 mesh to 600 mesh, and quartz sand with a grade of 40 mesh to 80 mesh, 80 mesh to 120 mesh and 100 mesh to 200 mesh.

[0053] Component B is composed of the following raw materials: a modified fatty amine curing agent (triethylenetetramine) in a mass ratio of 12:5:70:3, a tertiary amine accelerator (N,N-dimethylaniline), a thixotropic agent (fumed silica) and silicon micropowder with a grading of 400 mesh to 600 mesh.

[0054] Component C is composed of the following raw materials: a modified alicyclic amine curing agent (1,3-BAC) and an organic peroxide (cyclohexanone peroxide) in a mass ratio of 15:8.

[0055] The preparation method of the above-mentioned low-temperature high-activity epoxy splicing adhesive comprises the following steps: S1, weigh the raw materials of component A according to the designed ratio, add FeSO4 and CuSO4 into ethanol at 55°C, mix well, and obtain a transition metal ion salt solution; The amino multifunctional epoxy resin, bisphenol F epoxy resin, vinyl resin, transition metal ion salt solution, active diluent and silane coupling agent are mixed, and then a thixotropic agent, silicon micropowder and quartz sand are added and mixed evenly to obtain component A.

[0056] S2, weighing the raw materials of component B according to the designed ratio, mixing the modified fatty amine curing agent, the tertiary amine accelerator and the silicon powder, and then adding the thixotropic agent, mixing evenly, to obtain component B.

[0057] S3, weighing the raw materials of component C according to the designed ratio, mixing the modified alicyclic amine curing agent and the organic peroxide to obtain component C.

[0058] There is no restriction on the order between S1~S3.

[0059] S4. Weigh each component according to the designed ratio. Before use, premix component A with component B, then add component C and mix evenly to obtain low-temperature and high-activity epoxy splicing adhesive.

[0060] Example 3 This embodiment provides a low-temperature, high-activity epoxy splicing adhesive, which is composed of component A, component B, and component C in a mass ratio of 1.5:1:0.4. Component A is composed of the following raw materials: amino multifunctional epoxy resin (AFG-90MH) in a mass ratio of 30:9:25:4:5:8:3:120:100, bisphenol F epoxy resin (REF-170), vinyl resin (Ashland 411 bisphenol A epoxy vinyl resin), transition metal ion salt solution (glycerol solution containing 35wt% FeCl3, 35wt% FeCl2 and 35wt% CuCl2), active diluent (resorcinol diglycidyl ether), silane coupling agent (glycidyl trimethoxy silane), thixotropic agent (fumed silica), 400-600 mesh silicon micropowder and 80-120 mesh quartz sand.

[0061] Component B is composed of the following raw materials: a modified fatty amine curing agent (triethylenetetramine) in a mass ratio of 18:2:50:2, a tertiary amine accelerator (N,N-diethylaniline), a thixotropic agent (organic bentonite and polyamide wax of equal mass) and silica powder with a gradation of 400 mesh to 600 mesh.

[0062] Component C is composed of the following raw materials: a modified alicyclic amine curing agent (1,3-BAC) and an organic peroxide (benzoyl peroxide) in a mass ratio of 18:4.

[0063] The preparation method of the above-mentioned low-temperature high-activity epoxy splicing adhesive comprises the following steps: S1, weighing the raw materials of component A according to the designed ratio, adding FeCl3, FeCl2 and CuCl2 into glycerol at 45°C, mixing evenly, to obtain a transition metal ion salt solution; The amino multifunctional epoxy resin, bisphenol F epoxy resin, vinyl resin, transition metal ion salt solution, active diluent and silane coupling agent are mixed, and then a thixotropic agent, silicon micropowder and quartz sand are added and mixed evenly to obtain component A.

[0064] S2, weighing the raw materials of component B according to the designed ratio, mixing the modified fatty amine curing agent, the tertiary amine accelerator and the silicon powder, and then adding the thixotropic agent, mixing evenly, to obtain component B.

[0065] S3, weighing the raw materials of component C according to the designed ratio, mixing the modified alicyclic amine curing agent and the organic peroxide to obtain component C.

[0066] There is no restriction on the order between S1~S3.

[0067] S4. Weigh each component according to the designed ratio. Before use, premix component A with component B, then add component C and mix evenly to obtain low-temperature and high-activity epoxy splicing adhesive.

[0068] Example 4 This embodiment provides a low-temperature, high-activity epoxy splicing adhesive, which is composed of component A, component B, and component C in a mass ratio of 2.5:1:1.2. Component A is composed of the following raw materials: amino multifunctional epoxy resin (AFG-90, AG-70 or AFG-90MH) in a mass ratio of 25:10:30:2:10:6:5:90:150, bisphenol F epoxy resin (REF-170), vinyl resin (Ashland 411 bisphenol A epoxy vinyl resin), transition metal ion salt solution (methanol solution containing 20wt% MnSO4 and 25wt% NiSO4), active diluent (triethylene glycol diglycidyl ether), silane coupling agent (glycidyl trimethoxy silane), thixotropic agent (equal masses of fumed silica and organic bentonite), silicon micropowder with a grade of 400 mesh to 600 mesh, and quartz sand with a grade of 40 mesh to 80 mesh, 80 mesh to 120 mesh, and 100 mesh to 200 mesh.

[0069] Component B is composed of the following raw materials: modified fatty amine curing agent (triethylenetetramine) in a mass ratio of 10:8:78:4, tertiary amine accelerator (equal masses of N,N-dimethylaniline and N,N-diethylaniline), thixotropic agent (fumed silica) and silicon micropowder with a gradation of 400 mesh to 600 mesh.

[0070] Component C is composed of the following raw materials: a modified alicyclic amine curing agent (1,3-BAC) and an organic peroxide (2,4-dichlorobenzoyl peroxide) in a mass ratio of 20:3.

[0071] The preparation method of the above-mentioned low-temperature high-activity epoxy splicing adhesive comprises the following steps: S1, weigh the raw materials of component A according to the designed ratio, add MnSO4 and NiSO4 into methanol at 50°C, mix well, and obtain a transition metal ion salt solution; The amino multifunctional epoxy resin, bisphenol F epoxy resin, vinyl resin, transition metal ion salt solution, active diluent and silane coupling agent are mixed, and then a thixotropic agent, silicon micropowder and quartz sand are added and mixed evenly to obtain component A.

[0072] S2, weighing the raw materials of component B according to the designed ratio, mixing the modified fatty amine curing agent, the tertiary amine accelerator and the silicon powder, and then adding the thixotropic agent, mixing evenly, to obtain component B.

[0073] S3, weighing the raw materials of component C according to the designed ratio, mixing the modified alicyclic amine curing agent and the organic peroxide to obtain component C.

[0074] There is no restriction on the order between S1~S3.

[0075] S4. Weigh each component according to the designed ratio. Before use, premix component A with component B, then add component C and mix evenly to obtain low-temperature and high-activity epoxy splicing adhesive.

[0076] Example 5 This embodiment provides a low-temperature, high-activity epoxy splicing adhesive, which is composed of component A, component B, and component C in a mass ratio of 2.2:1:0.6. Component A is composed of the following raw materials: amino multifunctional epoxy resin (AFG-90, AG-70 or AFG-90MH) in a mass ratio of 50:6:15:6:6:2:7:80:130, bisphenol F epoxy resin (REF-170), vinyl resin (Ashland 411 bisphenol A epoxy vinyl resin), transition metal ion salt solution (ethanol solution containing 50wt% CoCl2, 45wt% MnCl2 and 50wt% NiSO4), active diluent (equal masses of tert-butylphenyl glycidyl ether and triethylene glycol diglycidyl ether), silane coupling agent (glycidoxypropyl trimethoxysilane), thixotropic agent (equal masses of fumed silica and polyamide wax), silicon micropowder with a grade of 400 mesh to 600 mesh, and quartz sand with a grade of 40 mesh to 80 mesh, 80 mesh to 120 mesh and 100 mesh to 200 mesh.

[0077] Component B is composed of the following raw materials: a modified fatty amine curing agent (triethylenetetramine) in a mass ratio of 20:7:42:5, a tertiary amine accelerator (equal masses of 2,4,6-tris(dimethylaminomethyl)phenol and N,N-diethylaniline), a thixotropic agent (equal masses of fumed silica and organic bentonite) and silicon micropowder with a grading of 400 mesh to 600 mesh.

[0078] Component C is composed of the following raw materials: a modified alicyclic amine curing agent (1,3-BAC) and an organic peroxide (methyl ethyl ketone peroxide and 2,4-dichlorobenzoyl peroxide in equal weights) in a mass ratio of 10:10.

[0079] The preparation method of the above-mentioned low-temperature high-activity epoxy splicing adhesive comprises the following steps: S1, weigh the raw materials of component A according to the designed ratio, add CoCl2, MnCl2 and NiSO4 into ethanol at 50°C, mix well, and obtain a transition metal ion salt solution; The amino multifunctional epoxy resin, bisphenol F epoxy resin, vinyl resin, transition metal ion salt solution, active diluent and silane coupling agent are mixed, and then a thixotropic agent, silicon micropowder and quartz sand are added and mixed evenly to obtain component A.

[0080] S2, weighing the raw materials of component B according to the designed ratio, mixing the modified fatty amine curing agent, the tertiary amine accelerator and the silicon powder, and then adding the thixotropic agent, mixing evenly, to obtain component B.

[0081] S3, weighing the raw materials of component C according to the designed ratio, mixing the modified alicyclic amine curing agent and the organic peroxide to obtain component C.

[0082] There is no restriction on the order between S1~S3.

[0083] S4. Weigh each component according to the designed ratio. Before use, premix component A with component B, then add component C and mix evenly to obtain low-temperature and high-activity epoxy splicing adhesive.

[0084] Comparative Example 1 This comparative example provides an epoxy splicing adhesive, which is composed of component A, component B and component C in a mass ratio of 2:1:1. The raw materials and proportions of component A, component B and component C are similar to those in Example 1, except that the transition metal ion salt solution is omitted in component A, and the tertiary amine accelerator is omitted in component B.

[0085] The preparation method of the above epoxy splicing adhesive is the same as that of Example 1, except that the corresponding raw materials are omitted from the addition of the components A and B, and will not be described in detail.

[0086] Comparative Example 2 This comparative example provides an epoxy splicing adhesive, which is composed of component A, component B and component C in a mass ratio of 2:1:1. The raw materials and proportions of component A, component B and component C are similar to those in Example 1, except that the transition metal ion salt solution is omitted in component A.

[0087] The preparation method of the above epoxy splicing adhesive is the same as Example 1 except that the corresponding raw materials are omitted from component A, and will not be repeated here.

[0088] Comparative Example 3 This comparative example provides an epoxy splicing adhesive, which is composed of component A, component B and component C in a mass ratio of 2:1:1. The raw materials and proportions of component A, component B and component C are similar to those in Example 1, except that: component A omits the addition of transition metal ion salt solution and vinyl resin, component B omits the addition of tertiary amine accelerator, and component C omits the addition of organic peroxide.

[0089] The preparation method of the above-mentioned epoxy splicing adhesive is the same as Example 1, except that the corresponding raw materials are omitted from the A component, the B component and the C component, and the remaining steps are not repeated here.

[0090] Comparative Example 4 This comparative example provides an epoxy splicing adhesive, which is composed of component A, component B and component C in a mass ratio of 2:1:1. The raw materials and proportions of component A, component B and component C are similar to those in Example 1, except that: component A omits the addition of transition metal ion salt solution and vinyl resin, and component C omits the addition of organic peroxide.

[0091] The preparation method of the above epoxy splicing adhesive is the same as that of Example 1, except that the corresponding raw materials are omitted for components A and C, and will not be described in detail.

[0092] Comparative Example 5 This comparative example provides an epoxy splicing adhesive, which is composed of component A, component B and component C in a mass ratio of 2:1:1. The raw materials and proportions of component A, component B and component C are similar to those in Example 1, except that: component A omits adding vinyl resin, and component C omits adding organic peroxide.

[0093] The preparation method of the above epoxy splicing adhesive is the same as Example 1 except that the corresponding raw materials are omitted from the addition of components A and C, and the remaining steps are not repeated here.

[0094] Comparative Example 6 This comparative example provides an epoxy splicing adhesive, which is composed of component A, component B and component C in a mass ratio of 2:1:1. The raw materials and proportions of component A, component B and component C are similar to those in Example 1, except that the organic peroxide is omitted in component C.

[0095] The preparation method of the above epoxy splicing adhesive is the same as Example 1 except that the corresponding raw materials are omitted from the C component, and the remaining steps are not repeated here.

[0096] Comparative Example 7 This comparative example provides an epoxy splicing adhesive, which is composed of component A, component B and component C in a mass ratio of 2:1:1. The raw materials and proportions of component A, component B and component C are similar to those in Example 1, except that the tertiary amine accelerator is omitted in component B.

[0097] The preparation method of the above epoxy splicing adhesive is the same as that of Example 1, except that the corresponding raw materials are omitted from the B component, and will not be repeated here.

[0098] Comparative Example 8 This comparative example provides an epoxy splicing adhesive, which is composed of component A, component B and component C in a mass ratio of 2:1:1. The raw materials and proportions of component A, component B and component C are similar to those in Example 1, except that the vinyl resin is omitted in component A.

[0099] The preparation method of the above epoxy splicing adhesive is the same as Example 1 except that the corresponding raw materials are omitted from component A, and will not be repeated here.

[0100] Verification test According to T / CECS 10080-2020 "Epoxy Adhesives for Prefabricated Segment Assembly", the construction performance (removal, stirring, bonding time), mechanical properties (12h, 24h and 7d compressive strength), aging resistance (resistance to moisture and heat, freeze-thaw resistance, fatigue stress resistance, long-term stress resistance) of the epoxy splicing adhesives provided in Examples 1 to 5 and Comparative Examples 1 to 8 were evaluated in a low temperature environment (-15°C to -5°C). The specific test results are shown in Tables 1 to 2.

[0101] Table 1 Performance test results of low temperature and high activity epoxy splicing adhesive in the embodiment

[0102] Table 2 Performance test results of epoxy splicing adhesive of comparative example

[0103] From the test results of Example 1 and Comparative Example 3, it can be found that the low-temperature high-activity epoxy splicing adhesive with a special dual-initiator promotion system has higher activity at low temperatures, which indicates that the dual-initiator system can promote the free radical polymerization reaction of the vinyl resin, increase the system temperature, and then promote the reaction of the epoxy resin-amine curing agent system, which ultimately manifests as a faster early strength development.

[0104] From the test results of Example 1 and Comparative Example 1, it can be found that it is difficult to promote the free polymerization of vinyl resin at low temperatures using a single initiator system, which indicates that organic peroxides have a decomposition temperature and are basically inactive at low temperatures, and thus there are no free radicals to promote the polymerization of vinyl.

[0105] From the test results of Comparative Examples 1-2 and Comparative Example 7, it can be found that the system containing tertiary amine accelerators can promote the decomposition of organic peroxides and then initiate the polymerization of vinyl resins, so the initial strength increases faster.

[0106] From the test results of Comparative Examples 3 to 6 and 8, it can be found that in the entire reaction system, if the self-polymerization reaction of the vinyl resin is not used as a built-in heat source, the overall degree of curing will be low due to the low activity of the epoxy resin-amine curing agent system at low temperatures.

[0107] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modification, equivalent substitution or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A low temperature and high activity epoxy splicing adhesive, characterized in that: The invention comprises the following raw materials: epoxy resin, amine curing agent, vinyl resin, transition metal ion salt solution, tertiary amine accelerator and organic peroxide.

2. The low temperature and high activity epoxy splicing adhesive according to claim 1, characterized in that: The epoxy resin includes amino multifunctional epoxy resin and bisphenol F type epoxy resin; The amine curing agent includes a modified fatty amine curing agent and a modified alicyclic amine curing agent.

3. The low temperature and high activity epoxy splicing adhesive according to claim 1, characterized in that: It includes component A, component B and component C; wherein, The component A comprises amino multifunctional epoxy resin, bisphenol F epoxy resin, vinyl resin, transition metal ion salt solution, active diluent, silane coupling agent, thixotropic agent, silicon powder and quartz sand in a mass ratio of (25-50):(5-10):(15-30):(2-6):(5-10):(2-8):(2-10):(80-120):(100-150); The B component includes a modified fatty amine curing agent, a tertiary amine accelerator, a thixotropic agent and silica powder in a mass ratio of (10-20):(2-8):(2-5):(40-80); The C component includes a modified alicyclic amine curing agent and an organic peroxide in a mass ratio of (10-20):(3-10).

4. The low temperature and high activity epoxy splicing adhesive as claimed in claim 3, characterized in that: The mass ratio of the A component, the B component and the C component is (1.5-2.5):1:(0.4-1.2).

5. The low temperature and high activity epoxy splicing adhesive according to any one of claims 1 to 4, characterized in that: The vinyl resin includes bisphenol A type epoxy vinyl resin; The tertiary amine accelerator includes at least one of 2,4,6-tris(dimethylaminomethyl)phenol, N,N-dimethylaniline or N,N-diethylaniline; The organic peroxide includes one of methyl ethyl ketone peroxide, cyclohexanone peroxide, benzoyl peroxide or 2,4-dichlorobenzoyl peroxide.

6. The low temperature and high activity epoxy splicing adhesive according to any one of claims 1 to 4, characterized in that: The transition metal ion salt in the transition metal ion salt solution includes at least one of chloride or sulfate corresponding to cobalt, iron, copper, manganese or nickel; The solvent of the transition metal ion salt solution includes at least one of methanol, ethanol or glycerol; The concentration of the transition metal ion salt solution is 20wt%-50wt%.

7. The low temperature and high activity epoxy splicing adhesive as claimed in claim 6, characterized in that: The transition metal ion salt includes at least one of CoCl2, FeSO4, FeCl3, FeCl2, CuSO4, CuCl2, MnSO4, MnCl2, NiSO4 or NiCl2.

8. The low temperature and high activity epoxy splicing adhesive according to any one of claims 2 to 4, characterized in that: The modified fatty amine curing agent includes triethylenetetramine; The modified alicyclic amine curing agent includes 1,3-bis(aminomethyl)cyclohexane.

9. The low temperature and high activity epoxy splicing adhesive as claimed in claim 3 or 4, characterized in that: The active diluent includes at least one of tert-butylphenyl glycidyl ether, octyl glycidyl ether, resorcinol diglycidyl ether or triethylene glycol diglycidyl ether; The silane coupling agent includes an epoxy silane coupling agent; The thixotropic agent includes at least one of fumed silica, organic bentonite or polyamide wax.

10. Application of the low-temperature, high-activity epoxy splicing adhesive according to any one of claims 1 to 9 in the reinforcement of wind power mixed tower structures.

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