High performance epoxy resin grouting material, preparation method and application thereof

Abstract

The application provides a high-performance epoxy resin grouting material and a preparation method and application thereof. The epoxy resin grouting material comprises three components A, B and C, and is mixed in a mass ratio of 100:(30-40):(650-980) during use. The component A comprises 100 parts of epoxy resin, 20-35 parts of active diluent, 1-2 parts of wetting dispersant and 0.3-1 part of defoaming agent. The component B comprises 100 parts of modified amine curing agent, 12-30 parts of amino-modified POSS and 5-15 parts of curing accelerator. 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, the prepared epoxy grouting material has large flowability, good grouting performance, good comprehensive strength, high compressive elastic modulus and far superior performance to traditional epoxy grouting materials. The introduced high-density black gold sand aggregate improves the density of the slurry, improves the bubble escaping efficiency of the slurry, reduces the bubble content of the system, improves the comprehensive compactness, and thus the mechanical strength and comprehensive performance are improved.

Description

TECHNICAL FIELD

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

[0002] Epoxy resin grouting material is widely used as bridge support grouting, equipment pedestal grouting and concrete repair and reinforcement material. However, the existing epoxy resin grouting material on the market has poor fluidity, low modulus of cured product, large difference between the modulus of the cured product and the modulus of concrete, high overall heat release during the curing process, and poor compactness due to the high content of bubbles in the system. In addition, the bubbles escaping to the surface during the grouting construction process can cause voids on the lower surface of the support or equipment, resulting in poor stress transmission to the foundation and 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 disclosed material is composed of three components A, B and C. Component A includes epoxy resin, cyclic carbonate and silane coupling agent. Component B is composed of fatty amine and polyether amine and accelerant. Component C is composed of quartz sand and cement. The product has the characteristics of fast strength development and high adhesion, but the overall bone content is low, the fluidity is general, the economy is not high (the bone content is low), and the final compressive strength is 90-120 MPa and the compressive elastic modulus is only 6-12 GPa, which cannot meet the use requirements in some special scenarios such as high-frequency and high-amplitude vibration service environment of large equipment.

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

[0005] Chinese patent CN103554843B discloses the index and construction method of track filling and secondary grouting epoxy grouting material. The disclosed material includes 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, and component C is composed of cement, heavy calcium powder, sand, talc powder, etc. The ratio of A:B:C is 80-100:15-100:80-400. The aggregate addition amount is relatively small in general, the comprehensive cost is relatively high, the compression elastic modulus of the material is relatively low, the deformation or creep is relatively high in some scenes, and the structural safety is affected. SUMMARY

[0006] In view of the problems of high heat release peak, many bubbles, low modulus, uneconomicalness when the aggregate addition amount is low, poor flowability when the aggregate content is high, etc. of the existing technology epoxy grouting material, the application 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 flowability, high strength, high density and high modulus under high aggregate content, and the preparation method is simple, convenient for construction, and has great application prospect.

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

[0008] The component A includes epoxy resin 100 parts, active diluent 20-35 parts, wetting dispersant 1-2 parts and defoaming agent 0.3-1 part in terms of mass fraction.

[0009] The component B includes modified amine curing agent 100 parts and amino-modified POSS 12-30 parts and curing accelerator 5-15 parts.

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

[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 / 100g, and the epoxy value of the bisphenol F epoxy resin is 0.44-0.55 mol / 100g. Specifically, the epoxy resins can be one or a mixture of two or more of the following in any proportion: 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 F44 (epoxy value 0.44 mol / 100g), bisphenol F epoxy resin F51 (epoxy value 0.51 mol / 100g), and bisphenol F epoxy resin F55 (epoxy value 0.55 mol / 100g).

[0013] The aforementioned reactive diluent is any one or a mixture of two or more of the following: butyl glycidyl ether, benzyl glycidyl ether, dodecyl diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether. The reactive diluent primarily functions to dilute and reduce viscosity.

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

[0015] The aforementioned defoamer is a silicone-based defoamer; preferably, the aforementioned silicone-based defoamer is BYK085 or Momentive TSA 750S.

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

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

[0018] The above-mentioned amino-modified POSS structure is shown in formula (i) or (ii):

[0019]

[0020] Where R1 is n is 1 to 3.

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

[0022] The preparation method of the above-mentioned amino-modified POSS includes the following steps: dissolving epoxy POSS powder in toluene and heating to 60℃±5℃; adding a fatty amine to the epoxy POSS toluene solution, then adding the accelerator DMP30, and heating to 70℃±5℃, stirring and reacting for 2-5 hours under nitrogen protection; and then removing the toluene solvent under vacuum at 75-85℃ to obtain amino-modified POSS.

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

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

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

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

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

[0028]

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

[0030]

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

[0032]

[0033] The aforementioned fatty amines are one or a mixture of two or more of diethylenetriamine, triethylenetetramine, and tetraethylenepentamine.

[0034] A high-performance epoxy resin grout is applied in the fields of building repair and reinforcement, such as bridge bearing grouting and equipment foundation grouting. When using it, first mix components A and B in a specific ratio until homogeneous, then add a certain proportion of component C and mix thoroughly. Mixing components A and B first ensures more complete curing and a better cured product.

[0035] This application has the following advantages over the prior art:

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

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

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

[0039] (4) The wetting and dispersing agent in this 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 black gold sand-epoxy slurry is higher than that of general epoxy grouting material. The buoyancy of the bubbles in the slurry before curing is greater. In addition, the defoamer is combined to improve the bubble release ability of the system, so the overall bubble release speed is better and the overall bubble content of the system is lower than that of general epoxy grouting material. Attached Figure Description

[0040] Figure 1 Example 1: X-ray 3D microscope image;

[0041] Figure 2 Comparative 2 X-ray 3D microscope images. Detailed Implementation

[0042] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort 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, specifically: bisphenol A epoxy resin E51 (epoxy value 0.51mol / 100g), bisphenol A epoxy resin E55 (epoxy value 0.55mol / 100g), bisphenol F epoxy resin F51 (epoxy value 0.51mol / 100g), and bisphenol F epoxy resin F55 (epoxy value 0.55mol / 100g).

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

[0045] The epoxy group POSS is a self-made T6 or T8 structure. The preparation method is based on the hydrolysis method in the literature (Liu Changjun, Cheng Zhijun, Li Xiaodong, Jiang Dazhi. Synthesis of POSS epoxy compounds [J]. Polymer Materials Science and Engineering, 2005, 23(4):84-86). The terminal group is 3-glycidylpropoxy. The defoamer is Momentive TSA 750S.

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

[0047] The modified amine curing agents were Linhua Institute 401, Changzhou Shanfeng 3639L1, and Huntsman D230;

[0048] The black gold sand of different mesh sizes was supplied by Lingshou County Suifeng Mineral Products Processing Co., Ltd.

[0049] The amino-modified POSS1-5 were synthesized as follows in the examples below:

[0050] Synthesis example one:

[0051] 40g of epoxy-based POSS T8 was dissolved in 360g of toluene, heated to 60±5℃, 100g of diethylenetriamine was added, and then 1.0g of DMP30 was added. The mixture was stirred evenly and heated to 70±5℃ under nitrogen protection for 3h of stirring reaction. The mixture was then heated to 80±5℃ and the toluene solvent was removed under vacuum to obtain amino-modified POSS1.

[0052] Synthesis example two:

[0053] 30g of epoxy-based POSS T8 was dissolved in 300g of toluene and heated to 60±5℃. 100g of triethylenetetramine and 0.7g of DMP30 were added and mixed evenly. The mixture was heated to 70±5℃ and stirred for 4h under nitrogen protection. The mixture was then heated to 80±5℃ and the toluene solvent was removed under vacuum to obtain amino-modified POSS2.

[0054] Synthesis example three:

[0055] 25g of epoxy-based POSS T8 was dissolved in 400g of toluene and heated to 60±5℃. 100g of tetraethylenepentamine and 1.25g of DMP30 were added. The mixture was heated to 70±5℃ and stirred for 5h under nitrogen protection. The mixture was then heated to 80±5℃ and the toluene solvent was removed under vacuum to obtain amino-modified POSS3.

[0056] Synthesis example four:

[0057] 20g of epoxy POSST8 was dissolved in 450g of toluene and heated to 60±5℃. 50g of triethylenetetramine and 50g of tetraethylenepentamine were added, followed by 1.2g of DMP30. The mixture was heated to 70±5℃ and stirred for 5h under nitrogen protection. The mixture was then heated to 80±5℃ and the toluene solvent was removed under vacuum to obtain amino-modified POSS4.

[0058] Synthesis example five:

[0059] 20g of epoxy POSST6 and 10g of epoxy PossT8 were dissolved in 390g of toluene and heated to 60±5℃. 20g of diethylenetriamine and 80g of tetraethylenepentamine were added, followed by 1.2g of DMP30. The mixture was heated to 70±5℃ and stirred for 4h under nitrogen protection. The mixture was then heated to 80±5℃, and the toluene solvent was removed under vacuum to obtain amino-modified POSS5.

[0060] The preparation method of high-performance epoxy resin grout is as follows:

[0061] (1) Epoxy resin, reactive diluent, defoamer and wetting and dispersing agent are mixed evenly in proportion to obtain component A;

[0062] (2) Dissolve epoxy POSS powder in toluene and heat to 60℃±5℃; add fatty amine to epoxy POSS toluene solution, add accelerator DMP30, and heat to 70℃±5℃. Under nitrogen protection, stir the reaction for 2-5 hours; then remove toluene solvent under vacuum at 75-85℃ to obtain amino-modified POSS for later use.

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

[0064] (4) Mix 525 cement and black gold sand powder of different mesh sizes evenly 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 stir evenly.

[0066] Before use, the above-mentioned high-performance epoxy resin grouting material undergoes step (5) and is then re-cured for 7 days to determine its compressive strength, compressive modulus, and density.

[0067] All parts in the examples and comparative examples are by weight. The amount of each component used in each example is shown in Table 1.

[0068] Table 1

[0069]

[0070]

[0071] The proportions and amounts of each component in each comparative example are shown in Table 2:

[0072] Table 2

[0073]

[0074]

[0075] Test Example 1:

[0076] The flowability, compressive strength, flexural strength, bond strength, compressive modulus, cured density, and bubble content of the epoxy grouting materials prepared in Examples 1-7 and Comparative Examples 1-3 were tested respectively.

[0077] The performance tests of epoxy grouting materials were conducted in accordance with the relevant provisions of JC / T 1130-2017 "Grouting Materials for Bridge Bearings". The material preparation and sample molding were carried out at 23±2℃ and 50±5% relative humidity, and the curing temperature was 23℃±2℃.

[0078] The flowability was tested according to GB / T50448 (the standard referenced in JC / T 1130-2017); the compressive and flexural strengths of the epoxy grout were tested according to the relevant methods in GB / T 17671 (the standard referenced in JC / T 1130-2017); the bond strength was tested according to JC / T907; the modulus of elasticity was tested according to DL / T5193; and the bubble content was analyzed using X-ray microscopy. The test results are shown in Table 3.

[0079] Table 3

[0080]

[0081] The test results of Comparative Example 1 and various embodiments show that the compressive strength and flexural strength of the material both decreased to a certain extent. This indicates that the lack of amino-modified POSS has a significant impact on the crosslinking density, overall strength, and toughness of the material. Introducing amino-modified POSS can effectively increase the overall mechanical properties of the material.

[0082] The test results of Comparative Example 2 and the various embodiments show that replacing black gold sand with 1.18mm quartz sand leads to a decrease in the fluidity of epoxy resin grout and a significant decrease in various mechanical properties. The test results of Comparative Example 3 and the various embodiments show that the presence of wetting and dispersing agents can increase the fluidity of epoxy grout and reduce the overall bubble content, thereby ensuring higher mechanical properties.

[0083] According to this application Figure 1 The image shown is an X-ray 3D microscope image from Example 1 (where black dots indicate the locations of air bubbles, the size of the black dots indicates the size of the air bubbles, and the scale bar ranges from 3.84 × 10⁻⁶). 5 ~2.5×10 9 μm 3 ), Figure 2 Comparative X-ray 3D microscope images (where black dots indicate bubble locations, and the size of the black dots indicates bubble size; scale bar range: 3.26 × 10⁻⁶) 5 ~8.86×10 9 μm 3 It can be clearly seen that the overall bubble size in Example 1 is relatively small and the bubble content is low, with a volume percentage of about 0.90%. In contrast, after the black gold sand system in Comparative Example 2 was replaced with ordinary quartz sand, the overall bubble content was significantly higher, with a bubble volume percentage of about 3.5%, indicating that the bubble content of the new black gold sand system was significantly reduced.

[0084] The aforementioned high-performance epoxy resin grouting materials have broad application prospects, including but not limited to applications in building repair and reinforcement fields such as bridge bearing grouting and equipment foundation grouting.

[0085] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which 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. By weight, component A comprises 100 parts epoxy resin, 20-35 parts reactive diluent, 1-2 parts wetting and dispersing agent, and 0.3-1 parts defoamer; 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 cement, 70-100 parts 150-200 mesh black gold sand, 100-150 parts 80-120 mesh black gold sand, 150-200 parts 20-40 mesh black gold sand, 100-150 parts 10-20 mesh black gold sand, and 60-100 parts 6-8 mesh black gold sand; The wetting and dispersing agent is an amphiphilic copolymer; The amino-modified POSS structure is shown in formula (i) or (ii): （i）， (ii), Where R1 is n is 1 to 3.

2. The 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 reactive diluent is any one or a mixture of two or more of butyl glycidyl ether, benzyl glycidyl ether, dodecyl diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether in any proportion.

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

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

5. The high-performance epoxy resin grouting material according to claim 4, characterized in that: The mass ratio of the fatty amine to the epoxy POSS is 100:(20~40).

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

7. The high-performance epoxy resin grouting material according to claim 4, characterized in that: The amount of the accelerator DMP30 is 0.5~1.0% of the total mass of epoxy POSS and fatty amine.

8. The application of the high-performance epoxy resin grouting material according to any one of claims 1-7 in the field of building repair and reinforcement.

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