High-performance epoxy resin grouting material as well as preparation method and application thereof

Abstract

The invention provides a high-performance epoxy resin grouting material as well as a preparation method and application thereof, the epoxy resin grouting material comprises a component A, a component B and a component C which are mixed according to a mass ratio of 100: (30-40): (650-980) during use; the component A comprises 100 parts of epoxy resin, 20-35 parts of a reactive diluent, 1-2 parts of a wetting dispersant and 0.3-1 part of a defoaming agent; the component B comprises 100 parts of a modified amine curing agent, 12-30 parts of amino modified POSS (Polyhedral Oligomeric Silsesquioxane) and 5-15 parts of a curing accelerator; and the component C comprises 100 parts of cement and black gold sand with different mesh numbers. The high-density, low-oil-absorption and high-strength black gold sand aggregate is introduced, so that the prepared epoxy grouting material has the advantages of high fluidity, good pouring performance, good comprehensive strength and high compressive elastic modulus, and the performance of the epoxy grouting material is far superior to that of a traditional epoxy grouting material. And the introduced high-density black gold sand aggregate improves the slurry density, improves the slurry bubble escape efficiency, reduces the bubble content of the system, and improves the comprehensive compactness, so that the mechanical strength and the comprehensive performance are improved.

Description

Technical Field

[0001] The invention relates to the technical field of grouting materials, and in particular to a high-performance epoxy resin grouting material and a preparation method and application thereof. Background Art

[0002] Epoxy resin grouting materials are widely used as bridge bearing grouting, equipment base grouting, and concrete repair and reinforcement materials. However, the epoxy resin grouting materials currently on the market have poor fluidity and low modulus of cured products, which is quite different from the elastic modulus of concrete. The overall heat release during the curing process is high, and the high content of bubbles in the system leads to poor compactness. In addition, during the grouting construction process, bubbles escape to the surface, which can easily cause the lower surface of the bearing or equipment to become empty, resulting in the failure of stress to be well transferred to the foundation, thus causing equipment failure and other safety accidents.

[0003] Chinese patent CN102898075A discloses a high-strength, fast-curing epoxy resin grouting material and a preparation method thereof. The material disclosed in the invention adopts three components A, B, and C. Component A includes epoxy resin, cyclocarbonate and silane coupling agent, component B is composed of fatty amine, polyether amine and accelerator, and component C is quartz sand and cement. The product has the characteristics of fast strength development and high adhesion, but its overall aggregate addition multiple is low, fluidity is general, and economy is not high (low aggregate content), and the ultimate compressive strength is 90-120MPa, and the compressive elastic modulus is only 6-12GPa. It is difficult to meet the use requirements in some special scenarios such as high-frequency and high-amplitude vibration service environments of large equipment.

[0004] Chinese patent CN105062004A discloses an epoxy grouting material for glass fiber sleeve reinforcement system and its preparation method. The material consists of three components A, B and C. Component A consists of epoxy resin, active diluent, toughening agent, silane coupling agent, defoamer, leveling agent, and active silicon powder. Component B is composed of cardanol modified phenolic amine curing agent. Component C consists of quartz sand, fly ash, and barite powder. The ratio of A, B, and C is 2:1:(2-10). The material has the characteristics of good curing in humid and water-containing environments, but it also has the problems of low aggregate consumption, general economy, and low elastic modulus.

[0005] Chinese patent CN103554843B discloses the indicators and construction methods of epoxy grouting materials for track filling and secondary grouting. The disclosed materials include three components A, B, and C. Component A is composed of modified epoxy resin, active diluent, toughening agent, antioxidant, leveling agent, defoaming agent, coupling agent, etc. Component B is composed of amine curing agent, component C is composed of cement, heavy calcium powder, sand, talcum powder, etc., A: B: C is 80-100: 15-100: 80-400. Overall, the amount of aggregate added is small, and the overall cost is high. At the same time, the material has a low compressive elastic modulus, and the deformation or creep is high in some scenarios, affecting the structural safety. Summary of the invention

[0006] In view of the problems of the prior art epoxy grouting materials such as high exothermic peak, many bubbles, low modulus, uneconomical when low aggregate addition is used, and poor fluidity when high aggregate content is used, the present invention provides a high-performance epoxy resin grouting material and a preparation method and application thereof. The epoxy resin grouting material has excellent properties such as high fluidity, high strength, high density, and high modulus at a high aggregate content. The preparation method of the present application is simple and the construction is convenient, and it has great application prospects.

[0007] A high-performance epoxy resin grouting material, the epoxy resin grouting material comprises three components A, B and C, which are mixed in a mass ratio of 100: (30-40): (650-980) when used;

[0008] Calculated by weight, component A includes 100 parts of epoxy resin, 20-35 parts of active diluent, 1-2 parts of wetting and dispersing agent, and 0.3-1 part of defoaming agent;

[0009] Component B includes 100 parts of modified amine curing agent, 12-30 parts of amino-modified POSS, and 5-15 parts of curing accelerator;

[0010] Component C includes 100 parts of cement, 70-100 parts of 150-200 mesh black gold sand, 100-150 parts of 80-120 mesh black gold sand, 150-200 parts of 20-40 mesh black gold sand, 100-150 parts of 10-20 mesh black gold sand, and 60-100 parts of 6-8 mesh black gold sand.

[0011] The epoxy resin is bisphenol A epoxy resin and / or bisphenol F epoxy resin, and the epoxy value of the epoxy resin is 0.44-0.55 mol / 100g;

[0012] Preferably, the epoxy value of the bisphenol A epoxy resin is 0.51-0.55 mol / 100 g, and the epoxy value of the bisphenol F epoxy resin is 0.44-0.55 mol / 100 g. Specifically, the optional epoxy resin is one or a mixture of any two or more of bisphenol A epoxy resin E51 (epoxy value 0.51 mol / 100 g), bisphenol A epoxy resin E55 (epoxy value 0.55 mol / 100 g), bisphenol F epoxy resin F44 (epoxy value 0.44 mol / 100 g), bisphenol F epoxy resin F51 (epoxy value 0.51 mol / 100 g), and bisphenol F epoxy resin F55 (epoxy value 0.55 mol / 100 g).

[0013] The above-mentioned active diluent is any one of butyl glycidyl ether, benzyl glycidyl ether, dodecyl diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butanediol diglycidyl ether, polypropylene glycol diglycidyl ether, or a mixture of two or more in any proportion. The active diluent mainly plays the role of diluting and reducing viscosity.

[0014] The above-mentioned wetting and dispersing agent is an amphiphilic copolymer; preferably, the above-mentioned wetting and dispersing agent is a wetting and dispersing agent such as BYK110 and Deqian 9250.

[0015] The above-mentioned defoaming agent is a silicone defoaming agent; preferably, the above-mentioned silicone defoaming agent is BYK085 or Momentive TSA 750S.

[0016] The modified amine curing agent is one of a phenolic amine curing agent or a polyether amine curing agent or a mixture of two or more in any ratio; preferably, the phenolic amine curing agent is the Institute of Forest Chemistry 401 curing agent, 400 curing agent, Changzhou Shanfeng 3639 curing agent; preferably, the polyether amine curing agent is Huntsman D220 curing agent, D230 curing agent, BASF EC301 curing agent.

[0017] The curing accelerator is one of 2,4,6-tris(dimethylaminomethyl)phenol (DMP30) and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or a mixture of two or more of them in any ratio.

[0018] The amino-modified POSS structure is as shown in the following formula (i) or (ii):

[0019]

[0020] Among them, R1 is n is 1 to 3.

[0021] Preferably, the amino-modified POSS structure is of formula (ii).

[0022] The preparation method of the amino-modified POSS comprises the following steps: dissolving epoxy POSS powder in toluene and heating to 60°C±5°C; adding aliphatic amine to the epoxy POSS toluene solution, adding accelerator DMP30, heating to 70°C±5°C, stirring and reacting for 2-5h under nitrogen protection; and removing the toluene solvent in vacuum at 75-85°C to obtain the amino-modified POSS.

[0023] The mass ratio of the above-mentioned fatty amine to the epoxy POSS is 100:(20-40).

[0024] The amount of toluene used is 2 to 4 times the total mass of the epoxy POSS and the fatty amine.

[0025] The amount of the accelerator DMP30 is 0.5-1.0% of the total mass of the epoxy POSS and the fatty amine.

[0026] The epoxy POSS is an epoxy polysilsesquioxane T6 structure or an epoxy polysilsesquioxane T8 structure; preferably, the epoxy POSS is an epoxy polysilsesquioxane T8 structure.

[0027] The structure of the epoxy polysilsesquioxane T6 is shown in formula (iii):

[0028]

[0029] The structure of the epoxy polysilsesquioxane T8 is shown in formula (iv):

[0030]

[0031] In the above structures of formula (iii) and formula (iv), R is 3-glycidyl propoxy, and the structural formula of R is as follows (v):

[0032]

[0033] The fatty amine is one of diethylenetriamine, triethylenetetramine and tetraethylenepentamine or a mixture of two or more thereof.

[0034] A high-performance epoxy resin grouting material is used in the fields of building repair and reinforcement such as bridge bearing grouting and equipment foundation grouting. When using, first mix components A and B in proportion and stir evenly, then add a certain proportion of component C and mix evenly. Mixing components A and B first makes the curing more complete and the curing effect better.

[0035] Compared with the prior art, this application has the following advantages:

[0036] (1) The present invention introduces high-density, low-oil-absorption, high-strength black gold sand aggregate, and the prepared epoxy grouting material has high fluidity, good pouring performance, good material comprehensive strength, high compressive elastic modulus, and its performance is far superior to traditional epoxy grouting materials.

[0037] (2) The high-density black gold sand aggregate introduced in the present invention increases the slurry density, thereby improving the slurry bubble escape efficiency, reducing the bubble content of the system, and increasing the overall density, thereby improving the mechanical strength and comprehensive performance.

[0038] (3) Amino-modified POSS can increase the comprehensive crosslinking density and overall impact toughness of the system, thereby increasing the comprehensive elastic modulus of the material. The dispersion and modification effects are far better than those of general POSS-modified epoxy resin.

[0039] (4) The wetting and dispersing agent in the present invention helps the black gold sand to be evenly dispersed in the slurry. Due to the high density of the black gold sand, the density of the formed black gold sand-epoxy slurry is higher than that of the general epoxy grouting material. The buoyancy of the bubbles in the slurry before curing is greater. Further combined with the defoaming agent, the system's defoaming ability is improved, so that the overall bubble defoaming speed is better, and the comprehensive bubble content of the system is lower than that of the general epoxy grouting material. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Figure 1 This is an X-ray 3D microscope photo of Example 1;

[0041] Figure 2 This is the X-ray 3D microscope photo of comparative example 2. DETAILED DESCRIPTION

[0042] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solution of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0043] Bisphenol A and bisphenol F epoxy resins are products of Nan Ya Resin Factory, including: bisphenol A epoxy resin E51 (epoxy value 0.51 mol / 100g), bisphenol A epoxy resin E55 (epoxy value 0.55 mol / 100g), bisphenol F epoxy resin F51 (epoxy value 0.51 mol / 100g), bisphenol F epoxy resin F55 (epoxy value 0.55 mol / 100g);

[0044] The epoxy diluents are butyl glycidyl ether (501, epoxy value 0.59-0.63 mol / 100 g), benzyl glycidyl ether (692, epoxy value 0.54-0.58 mol / 100 g), and dodecyl glycidyl ether (AGE, epoxy value 0.34-0.38 mol / 100 g), provided by Anhui Xinyuan Technology Co., Ltd.; ethylene glycol diglycidyl ether (HY669, epoxy value 0.7-0.8 mol / 100 g), butanediol diglycidyl ether (HY622, epoxy value 0.74-0.83 mol / 100 g) are provided by Shanghai Rufa Chemical Technology Co., Ltd.;

[0045] The epoxy POSS was a self-made T6 or T8 structure, prepared by hydrolysis method according to the literature (Liu Changjun, Cheng Zhijun, Li Xiaodong, Jiang Dazhi. Synthesis of POSS Epoxides [J]. Polymer Materials Science and Engineering, 2005, 23(4): 84-86), and the top group was 3-glycidyl propoxy; the defoaming agent was Maitu TSA 750S;

[0046] The wetting and dispersing agent is BYK110 wetting and dispersing agent;

[0047] The modified amine curing agents are 401 from the Institute of Forest Chemistry, 3639L1 from Changzhou Shanfeng, and D230 from Huntsman;

[0048] Black gold sand of different mesh sizes is provided by Lingshou County Suifeng Mineral Products Processing Co., Ltd.

[0049] In the following examples, amino-modified POSS1-5 were synthesized as follows:

[0050] Synthesis example one:

[0051] Take 40g of epoxy POSS T8 and dissolve it in 360g of toluene, heat it to 60±5℃, add 100g of diethylenetriamine, then add 1.0g of DMP30, mix and stir evenly, heat it to 70±5℃ and stir and react for 3h under nitrogen protection, heat it to 80±5℃, remove the toluene solvent in vacuo to obtain amino-modified POSS1.

[0052] Synthesis example two:

[0053] Take 30g of epoxy POSS T8 and dissolve it in 300g of toluene, heat it to 60±5℃, add 100g of triethylenetetramine, then add 0.7g of DMP30, mix and stir evenly, heat it to 70±5℃ and stir and react for 4h under nitrogen protection, heat it to 80±5℃, remove the toluene solvent in vacuo to obtain amino-modified POSS2.

[0054] Synthesis example three:

[0055] Take 25g of epoxy POSS T8 and dissolve it in 400g of toluene, heat it to 60±5℃, add 100g of tetraethylenepentamine, then add 1.25g of DMP30, heat it to 70±5℃ and stir it under nitrogen protection for 5h, heat it to 80±5℃, remove the toluene solvent in vacuo to obtain amino-modified POSS3.

[0056] Synthesis example four:

[0057] Take 20g of epoxy POSST8 and dissolve it in 450g of toluene, heat it to 60±5℃, add 50g of triethylenetetramine, add 50g of tetraethylenepentamine, and then add 1.2g of DMP30, heat it to 70±5℃ and stir it under nitrogen protection for 5h, heat it to 80±5℃, remove the toluene solvent in vacuo to obtain amino-modified POSS4.

[0058] Synthesis example five:

[0059] Take 20g of epoxy POSST6 and 10g of epoxy PossT8 and dissolve them in 390g of toluene, heat to 60±5℃, add 20g of diethylenetriamine, add 80g of tetraethylenepentamine, and then add 1.2g of DMP30, heat to 70±5℃, stir and react under nitrogen protection for 4h, heat to 80±5℃, remove the toluene solvent in vacuo, and obtain amino-modified POSS5.

[0060] The preparation method of high performance epoxy resin grouting material is as follows:

[0061] (1) mixing epoxy resin, active diluent, defoamer and wetting dispersant in proportion to obtain component A;

[0062] (2) dissolving epoxy POSS powder in toluene and heating to 60°C±5°C; adding aliphatic amine to the epoxy POSS toluene solution, adding accelerator DMP30, and heating to 70°C±5°C, stirring and reacting for 2-5h under nitrogen protection; then removing the toluene solvent in vacuum at 75-85°C to obtain amino-modified POSS for standby use;

[0063] (3) mixing the modified amine curing agent, the amino-modified POSS, and the curing accelerator in proportion to obtain component B;

[0064] (4) 525 cement and black gold sand powder of different mesh sizes are mixed and stirred to obtain component C;

[0065] (5) When using, first mix components A and B in proportion and stir evenly, then add a certain proportion of component C and mix evenly.

[0066] The high-performance epoxy resin grouting material is subjected to step (5) before use, and then molded and cured for 7 days to measure its compressive strength, compressive elastic modulus and density.

[0067] All parts in the examples and comparative examples are parts by mass. The parts and amounts of each component in each example are shown in Table 1:

[0068] Table 1

[0069]

[0070]

[0071] The amount of each component in each comparative example is shown in Table 2:

[0072] Table 2

[0073]

[0074]

[0075] Test Example 1:

[0076] The epoxy grouting materials prepared in Examples 1-7 and Comparative Examples 1-3 were tested for fluidity, compressive strength, flexural strength, bonding strength, compressive elastic modulus, and cured material density and bubble content.

[0077] Some performance tests of epoxy grouting materials are carried out in accordance with the relevant provisions of JC / T 1130-2017 "Bridge Support Grouting Materials". Material preparation and sample molding are 23±2℃, relative humidity is 50±5%, and curing temperature is 23℃±2℃.

[0078] The fluidity is tested according to GB / T50448 (referenced standard in JC / T 1130-2017); the compression and flexural strength of epoxy grouting materials are tested according to the relevant methods in GB / T 17671 (referenced standard in JC / T 1130-2017); the bonding strength is tested according to JC / T907; the elastic modulus is tested according to DL / T5193; the bubble content is analyzed by X-ray microscope. The above test results are shown in Table 3:

[0079] Table 3

[0080]

[0081] Through the test results of comparative example 1 and each embodiment, it can be seen that the compressive strength and flexural strength of the material are both decreased to a certain extent, indicating that the lack of amino-modified POSS has a significant effect on the crosslinking density, comprehensive strength and toughness of the material. The introduction of amino-modified POSS can effectively increase the comprehensive mechanical properties of the material.

[0082] Through the test results of Example 2 and each embodiment, it can be seen that the replacement of black gold sand with 1.18 mm quartz sand leads to a decrease in the fluidity of the epoxy resin grouting material and a significant decrease in various mechanical properties; the test results of Example 3 and each embodiment show that the presence of the wetting dispersant can increase the fluidity of the epoxy grouting material and reduce the overall bubble content, thereby ensuring higher mechanical properties.

[0083] According to this application Figure 1 This is an X-ray 3D microscope photo of Example 1 (the black dots are the locations of the bubbles, the size of the black dots indicates the size of the bubbles, and the scale range is 3.84×10 5 ~2.5×10 9 μm 3 ), Figure 2 This is the X-ray 3D microscope photo of Comparative Example 2 (the black dots are the locations of the bubbles, the size of the black dots indicates the size of the bubbles, and the scale range is 3.26×10 5 ~8.86×10 9 μm 3 ), it can be clearly seen that the overall bubble size of Example 1 is smaller, and the bubble content is lower, about 0.90% by volume, while in Comparative Example 2, after the black gold sand system is replaced with ordinary quartz sand, the overall bubble content is significantly higher, about 3.5% by volume, indicating that the bubble content of the new black gold sand system is significantly reduced.

[0084] The above-mentioned high-performance epoxy resin grouting material has broad application prospects, including but not limited to bridge bearing grouting, equipment foundation grouting and other building repair and reinforcement fields.

[0085] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A high performance epoxy resin grouting material, characterized in that: The epoxy resin grouting material comprises three components A, B and C, which are mixed in a mass ratio of 100: (30-40): (650-980) when used; Calculated by weight, component A includes 100 parts of epoxy resin, 20-35 parts of active diluent, 1-2 parts of wetting and dispersing agent, and 0.3-1 part of defoaming agent; Component B includes 100 parts of modified amine curing agent, 12-30 parts of amino-modified POSS, and 5-15 parts of curing accelerator; Component C includes 100 parts of cement, 70-100 parts of 150-200 mesh black gold sand, 100-150 parts of 80-120 mesh black gold sand, 150-200 parts of 20-40 mesh black gold sand, 100-150 parts of 10-20 mesh black gold sand, and 60-100 parts of 6-8 mesh black gold sand.

2. A high performance epoxy resin grouting material according to claim 1, characterized in that: The epoxy resin is bisphenol A epoxy resin and / or bisphenol F epoxy resin, and the epoxy value of the epoxy resin is 0.44-0.55 mol / 100g; the active diluent is any one of butyl glycidyl ether, benzyl glycidyl ether, dodecyl diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butanediol diglycidyl ether, and polypropylene glycol diglycidyl ether, or a mixture of two or more in any proportion.

3. A high performance epoxy resin grouting material according to claim 1, characterized in that: The wetting and dispersing agent is an amphiphilic copolymer.

4. A high performance epoxy resin grouting material according to claim 1, characterized in that: The defoaming agent is a silicone defoaming agent; the modified amine curing agent is one of a phenolic amine curing agent or a polyether amine curing agent or a mixture of two or more in any proportion; the curing accelerator is one of 2,4,6-tris(dimethylaminomethyl)phenol (DMP30) and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or a mixture of two or more in any proportion.

5. The high performance epoxy resin grouting material according to claim 1, characterized in that: The amino-modified POSS structure is as shown in the following formula (i) or (ii): Among them, R1 is n is 1 to 3.

6. A high performance epoxy resin grouting material according to claim 1, characterized in that: The preparation method of the amino-modified POSS comprises the following steps: dissolving epoxy POSS powder in toluene and heating to 60°C±5°C; adding aliphatic amine to the epoxy POSS toluene solution, adding accelerator DMP30, heating to 70°C±5°C, stirring and reacting for 2-5h under nitrogen protection; and removing the toluene solvent in vacuum at 75-85°C to obtain the amino-modified POSS.

7. A high performance epoxy resin grouting material according to claim 6, characterized in that: The mass ratio of the fatty amine to the epoxy POSS is 100:(20-40).

8. The high performance epoxy resin grouting material according to claim 6, characterized in that: The amount of toluene used is 2 to 4 times the total mass of the epoxy POSS and the fatty amine.

9. A high performance epoxy resin grouting material according to claim 6, characterized in that: The amount of the accelerator DMP30 is 0.5-1.0% of the total mass of the epoxy POSS and the fatty amine.

10. The high-performance epoxy resin grouting material according to any one of claims 1 to 9 is used in the fields of building repair and reinforcement such as bridge bearing grouting and equipment foundation grouting.

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