Grouting hole sealing material and preparation method thereof

Abstract

The invention relates to the technical field of grouting and hole sealing materials, and discloses a grouting and hole sealing material and a preparation method thereof.The preparation method comprises the steps that pyromellitic dianhydride and bis (2-chloroethyl) amine serve as monomers and are subjected to an acylation reaction to obtain an intermediate product 1, then the intermediate product 1 and aminopropyltriethoxysilane are subjected to a substitution reaction to obtain silane-terminated hyperbranched polyamide, and the silane-terminated hyperbranched polyamide is subjected to a reaction to obtain the grouting and hole sealing material. The preparation method is simple, the structure is novel, raw materials are simple and easy to obtain, silane-terminated hyperbranched polyamide and 1, 3-propane sultone are used for reacting to obtain silane-terminated polysulfonate hyperbranched polyamide, finally, cement, epoxy resin, a curing agent, a defoaming agent, the silane-terminated polysulfonate hyperbranched polyamide and the like are added into deionized water, stirring and mixing are conducted to be uniform, and the high-performance water-based adhesive is obtained. The grouting hole sealing material is obtained. The grouting and hole sealing material prepared by the preparation method disclosed by the invention has relatively good mechanical properties and flowing properties.

Description

Technical Field

[0001] The invention relates to the technical field of grouting and sealing materials, in particular to a grouting and sealing material and a preparation method thereof. Background Art

[0002] Many cities are located along the Yangtze River and its main tributaries. There are a large number of river-related projects in urban construction, water conservancy, railways, roads, etc. During the early survey and later construction of these projects, a large number of drillings occurred within the levee management area. These drillings destroyed the geological structure and seepage conditions of the levee and levee foundation, posing a safety hazard to the levee. If they are not properly blocked, it is very easy to cause seepage damage such as soil flow and pipe bursting during the flood season, and there is even a risk of levee breach, seriously affecting the safety of people's lives and property.

[0003] The purpose of grouting and sealing is to fill and seal geological boreholes with slurry. The grouting and sealing materials are selected based on the grouting materials. There are two types of grouting materials used in water conservancy projects: one is a suspension slurry made of solid materials such as cement, clay, fly ash and sand; the other is a solution slurry made of chemical grouting materials such as formaldehyde, epoxy resin, and cyanide coagulant. Epoxy grouting material is a high-molecular chemical grouting material with high strength and strong adhesion. However, ordinary epoxy resin has great brittleness after curing, resulting in poor impact resistance and easy cracking, which is not conducive to its use in water conservancy projects. Based on this, the present invention compounds epoxy resin with cement materials to prepare a grouting and sealing material with good mechanical properties and fluidity. Summary of the invention

[0004] 1. Technical issues to be resolved

[0005] In view of the deficiencies in the prior art, the present invention provides a grouting and sealing material and a preparation method thereof, and the prepared grouting and sealing material has good mechanical properties and flow properties.

[0006] (II) Technical solution

[0007] To achieve the above objectives, the present invention is implemented through the following technical solutions:

[0008] A grouting and sealing material, the grouting and sealing material is composed of the following components by weight: 100 parts of cement, 2-10 parts of waterborne epoxy resin, 5-15 parts of bentonite, 2-6 parts of terminal silane hyperbranched polyamide, 1-3 parts of defoamer, 15-25 parts of expansion agent, 0.1-0.5 parts of terminal silane polysulfonate hyperbranched polyamide, and 30-50 parts of deionized water;

[0009] The preparation method of the grouting sealing material is as follows:

[0010] Add cement, waterborne epoxy resin, bentonite, and terminal silane hyperbranched polyamide to deionized water, stir and mix for 5-10 minutes, then add defoamer, expansion agent, and terminal silane polysulfonate hyperbranched polyamide, and continue stirring for 5-10 minutes to obtain a grouting sealing material;

[0011] The preparation method of the silane-terminated hyperbranched polyamide is:

[0012] (1) Under nitrogen protection, pyromellitic anhydride and bis(2-chloroethyl)amine were added to N,N-dimethylacetamide solvent, stirred and dissolved, and reacted at room temperature for 3-5 hours. After the reaction was completed, toluene was precipitated and rotary evaporated to obtain intermediate 1;

[0013] (2) The intermediate product 1 and aminopropyltriethoxysilane are added to N,N-dimethylacetamide solvent, stirred and dispersed, and the pH is adjusted to 7-9 with saturated sodium carbonate. The reaction is carried out at 40-55° C. for 6-12 hours. After the reaction is completed, the reaction is filtered and the solvent is evaporated to obtain terminal silane hyperbranched polyamide.

[0014] Preferably, the defoaming agent is P803 defoaming agent, and the swelling agent is UEA swelling agent.

[0015] Preferably, in (1), the molar ratio of pyromellitic anhydride to bis(2-chloroethyl)amine is 1:4.2-5.

[0016] Preferably, in (2), the molar ratio of the intermediate product 1 to aminopropyltriethoxysilane is 1:7.8-8.4.

[0017] Preferably, the preparation method of the terminal silane polysulfonate hyperbranched polyamide is:

[0018] Add terminal silane hyperbranched polyamide and 1,3-propane sultone into methanol solvent, stir and mix evenly, heat to 60-70°C, react for 24-48 hours, and after the reaction, add sodium carbonate, continue stirring for 1-3 hours, filter, distill under reduced pressure, and dry to obtain terminal silane polysulfonate hyperbranched polyamide.

[0019] Preferably, the molar ratio of the terminal silane hyperbranched polyamide, 1,3-propane sultone and sodium carbonate is 1:8.5-10:8-8.5.

[0020] (III) Beneficial technical effects

[0021] The present invention uses pyromellitic anhydride and bis(2-chloroethyl)amine as monomers, undergoes acylation reaction, obtains intermediate product 1, then carries out substitution reaction with aminopropyltriethoxysilane to obtain terminal silane hyperbranched polyamide, uses secondary amine contained in terminal silane hyperbranched polyamide to cure epoxy resin, introduces silane structure into epoxy resin; uses secondary amine contained in terminal silane hyperbranched polyamide to carry out ring-opening alkylation reaction with 1,3-propane sultone to obtain terminal silane polysulfonate hyperbranched polyamide. Finally, cement, epoxy resin, curing agent, defoamer, terminal silane polysulfonate hyperbranched polyamide and the like are added to deionized water, stirred and mixed evenly, and a grouting and sealing material is obtained.

[0022] The invention uses pyromellitic anhydride, bis(2-chloroethyl)amine, aminopropyltriethoxysilane and the like as raw materials and prepares terminal silane hyperbranched polyamide through two-step reactions. The terminal silane hyperbranched polyamide is used twice to react with epoxy resin and 1,3-propane sultone in sequence. The preparation method is simple, the structure is novel, the raw materials are simple and easily available, and the cost is reduced.

[0023] The present invention reacts the terminal silane hyperbranched polyamide with epoxy resin, and since the terminal silane hyperbranched polyamide contains multiple reaction sites, when it reacts with epoxy resin, a huge cross-linked network structure can be formed. In the reaction process, the silane structure is introduced into the epoxy resin, and silane hydrolysis is utilized to produce a silicon oxygen bond, which is condensed with the hydroxyl group on the cement surface, and the epoxy resin is firmly attached to the surface of the cement, and then a layer of film is formed, and this layer of polymer film can not only prevent the contact of cement with water, but also increase the hydration layer thickness of cement, reduce the viscosity of the grouting and sealing material, and then improve the fluidity of the grouting and sealing material, and this layer of polymer film can reduce the space and defect of the grouting and sealing material, that is, the space and defect of the grouting and sealing material are filled and reinforced, and then the mechanical property of the grouting and sealing material is improved. In addition, when the material is hardened and subjected to external force, the huge cross-linked network structure contained therein can absorb and transfer energy, and further improves the mechanical property of the grouting and sealing material.

[0024] The present invention reacts terminal silane hyperbranched polyamide with 1,3-propane sultone to prepare a terminal silane polysulfonate hyperbranched polyamide, wherein the silane structure can be hydrolyzed to condense with the hydroxyl group on the cement surface to firmly adhere to the cement surface, and the sulfonate therein, as a hydrophilic group, will overlap and repel each other to produce a steric hindrance, so that the cement is dispersed and not cohesive, the fluidity of the grouting and sealing material is improved, the water consumption is reduced, the porosity of the grouting and sealing material is reduced after hardening, and the mechanical property is improved.

[0025] In addition, the present invention uses bentonite as a stabilizer. Bentonite particles are finer than cement particles and can fill tiny cracks and pores, increase the density of the grouting and sealing material, and improve the mechanical properties of the grouting and sealing material. The grouting and sealing material prepared by the present invention has good mechanical properties and flow properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 It is the reaction route of silane-terminated hyperbranched polyamide;

[0027] Figure 2 It is the reaction route of terminal silane polysulfonate hyperbranched polyamide;

[0028] Figure 3 This is the SEM image of the sample of Example 4. DETAILED DESCRIPTION

[0029] In order to make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are 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.

[0030] The cement was PO42.5 ordinary Portland cement produced by Huaxin Cement Plant;

[0031] The bentonite used is calcium-based bentonite produced by Zaoyang Bentonite Factory.

[0032] Example 1

[0033] (1) Under nitrogen protection, 0.05 mol of pyromellitic anhydride and 0.21 mol of bis(2-chloroethyl)amine were added to N,N-dimethylacetamide solvent, stirred and dissolved, and reacted at room temperature for 4 hours. After the reaction was completed, toluene was precipitated and rotary evaporated to obtain intermediate 1.

[0034] (2) 0.05 mol of the intermediate product 1 and 0.4 mol of aminopropyltriethoxysilane were added to N,N-dimethylacetamide solvent, stirred and dispersed, and the pH was adjusted to 8 with saturated sodium carbonate. The reaction was carried out at 55° C. for 10 h. After the reaction was completed, the reaction was filtered and the solvent was evaporated to obtain terminal silane hyperbranched polyamide.

[0035] (3) Add 10 mmol of terminal silane hyperbranched polyamide and 100 mmol of 1,3-propane sultone into methanol solvent, stir and mix evenly, heat to 65°C, react for 36 hours, and after the reaction, add 85 mmol of sodium carbonate, continue stirring for 3 hours, filter, distill under reduced pressure, and dry to obtain terminal silane polysulfonate hyperbranched polyamide.

[0036] (4) 1000 g of cement, 20 g of water-based epoxy resin, 50 g of bentonite, and 20 g of terminal silane hyperbranched polyamide were added to 500 g of deionized water, stirred and mixed for 5 min, and then 30 g of P803 defoamer, 200 g of UEA expansion agent, and 1 g of terminal silane polysulfonate hyperbranched polyamide were added thereto, and stirring was continued for 5 min to obtain a grouting sealing material.

[0037] Example 2

[0038] (1) Under nitrogen protection, 0.05 mol of pyromellitic anhydride and 0.25 mol of bis(2-chloroethyl)amine were added to N,N-dimethylacetamide solvent, stirred and dissolved, and reacted at room temperature for 3 h. After the reaction was completed, toluene was precipitated and rotary evaporated to obtain intermediate 1.

[0039] (2) 0.05 mol of the intermediate product 1 and 0.42 mol of aminopropyltriethoxysilane were added to N,N-dimethylacetamide solvent, stirred and dispersed, and the pH was adjusted to 9 with saturated sodium carbonate. The reaction was carried out at 45° C. for 10 h. After the reaction was completed, the reaction was filtered and the solvent was evaporated to obtain terminal silane hyperbranched polyamide.

[0040] (3) Add 10 mmol of terminal silane hyperbranched polyamide and 90 mmol of 1,3-propane sultone into methanol solvent, stir and mix evenly, heat to 65°C, react for 48 hours, and after the reaction, add 85 mmol of sodium carbonate, continue stirring for 2 hours, filter, distill under reduced pressure, and dry to obtain terminal silane polysulfonate hyperbranched polyamide.

[0041] (4) 1000 g of cement, 40 g of water-based epoxy resin, 80 g of bentonite, and 30 g of terminal silane hyperbranched polyamide were added to 400 g of deionized water, and the mixture was stirred for 10 min. Then, 20 g of P803 defoamer, 250 g of UEA expansion agent, and 2 g of terminal silane polysulfonate hyperbranched polyamide were added thereto, and stirring was continued for 10 min to obtain a grouting sealing material.

[0042] Example 3

[0043] (1) Under nitrogen protection, 0.05 mol of pyromellitic anhydride and 0.24 mol of bis(2-chloroethyl)amine were added to N,N-dimethylacetamide solvent, stirred and dissolved, and reacted at room temperature for 5 h. After the reaction was completed, toluene was precipitated and rotary evaporated to obtain intermediate 1.

[0044] (2) 0.05 mol of the intermediate product 1 and 0.39 mol of aminopropyltriethoxysilane were added to N,N-dimethylacetamide solvent, stirred and dispersed, and the pH was adjusted to 9 with saturated sodium carbonate. The reaction was carried out at 45° C. for 12 h. After the reaction was completed, the reaction was filtered and the solvent was evaporated to obtain terminal silane hyperbranched polyamide.

[0045] (3) Add 10 mmol of terminal silane hyperbranched polyamide and 90 mmol of 1,3-propane sultone into methanol solvent, stir and mix evenly, heat to 60°C, and react for 48 hours. After the reaction is completed, add 85 mmol of sodium carbonate, continue stirring for 3 hours, filter, distill under reduced pressure, and dry to obtain terminal silane polysulfonate hyperbranched polyamide.

[0046] (4) 1000 g of cement, 60 g of water-based epoxy resin, 100 g of bentonite, and 40 g of terminal silane hyperbranched polyamide were added to 300 g of deionized water, stirred and mixed for 8 min, and then 10 g of P803 defoamer, 150 g of UEA expansion agent, and 3 g of terminal silane polysulfonate hyperbranched polyamide were added thereto, and stirring was continued for 8 min to obtain a grouting sealing material.

[0047] Example 4

[0048] (1) Under nitrogen protection, 0.05 mol of pyromellitic anhydride and 0.24 mol of bis(2-chloroethyl)amine were added to N,N-dimethylacetamide solvent, stirred and dissolved, and reacted at room temperature for 5 h. After the reaction was completed, toluene was precipitated and rotary evaporated to obtain intermediate 1.

[0049] (2) 0.05 mol of the intermediate product 1 and 0.42 mol of aminopropyltriethoxysilane were added to N,N-dimethylacetamide solvent, stirred and dispersed, and the pH was adjusted to 7 with saturated sodium carbonate. The reaction was carried out at 55° C. for 10 h. After the reaction was completed, the reaction was filtered and the solvent was evaporated to obtain terminal silane hyperbranched polyamide.

[0050] (3) Add 10 mmol of terminal silane hyperbranched polyamide and 85 mmol of 1,3-propane sultone into methanol solvent, stir and mix evenly, heat to 70°C, react for 24 hours, and after the reaction, add 80 mmol of sodium carbonate, continue stirring for 1 hour, filter, distill under reduced pressure, and dry to obtain terminal silane polysulfonate hyperbranched polyamide.

[0051] (4) 1000 g of cement, 80 g of water-based epoxy resin, 120 g of bentonite, and 50 g of terminal silane hyperbranched polyamide were added to 400 g of deionized water, stirred and mixed for 8 min, and then 20 g of P803 defoamer, 220 g of UEA expansion agent, and 4 g of terminal silane polysulfonate hyperbranched polyamide were added thereto, and stirring was continued for 8 min to obtain a grouting sealing material.

[0052] Example 5

[0053] (1) Under nitrogen protection, 0.05 mol of pyromellitic anhydride and 0.22 mol of bis(2-chloroethyl)amine were added to N,N-dimethylacetamide solvent, stirred and dissolved, and reacted at room temperature for 4 hours. After the reaction was completed, toluene was precipitated and rotary evaporated to obtain intermediate 1.

[0054] (2) 0.05 mol of the intermediate product 1 and 0.4 mol of aminopropyltriethoxysilane were added to N,N-dimethylacetamide solvent, stirred and dispersed, and the pH was adjusted to 8 with saturated sodium carbonate. The reaction was carried out at 40° C. for 6 h. After the reaction was completed, the reaction was filtered and the solvent was evaporated to obtain terminal silane hyperbranched polyamide.

[0055] (3) Add 10 mmol of terminal silane hyperbranched polyamide and 100 mmol of 1,3-propane sultone into methanol solvent, stir and mix evenly, heat to 65°C, react for 48 hours, and after the reaction, add 80 mmol of sodium carbonate, continue stirring for 2 hours, filter, distill under reduced pressure, and dry to obtain terminal silane polysulfonate hyperbranched polyamide.

[0056] (4) 1000 g of cement, 100 g of water-based epoxy resin, 150 g of bentonite, and 60 g of terminal silane hyperbranched polyamide were added to 500 g of deionized water, stirred and mixed for 6 min, and then 25 g of P803 defoamer, 180 g of UEA expansion agent, and 5 g of terminal silane polysulfonate hyperbranched polyamide were added thereto, and stirring was continued for 10 min to obtain a grouting sealing material.

[0057] Comparative Example 1

[0058] The difference between this comparative example and Example 1 is that step (4) does not contain waterborne epoxy resin, terminal silane hyperbranched polyamide and terminal silane polysulfonate hyperbranched polyamide.

[0059] Refer to GB / T2419-2005 to measure the flow properties of grouting and sealing materials.

[0060] Table 1:

[0061] Fluidity(mm) Example 1 360 Example 2 488 Example 3 583 Example 4 695 Example 5 655 Comparative Example 1 285

[0062] It can be seen from the table that the grouting and sealing material prepared by the present invention has good flowability.

[0063] The grouting sealing material was placed in a mold, and allowed to stand for 48 hours at 20°C and 50% relative humidity to form. The mold was then cured in a standard curing box at 20°C and 95% relative humidity for 28 days to obtain a sample.

[0064] Referring to DL / T5126-2001, a universal testing machine was used to test the mechanical properties of the specimens. The specimen size was 50 mm × 50 mm × 200 mm, and the loading rate of the universal testing machine was 0.1 mm / s.

[0065] Table 2:

[0066] Compressive strength(M Pa) Example 1 36.4 Example 2 42.6 Example 3 43.9 Example 4 45.0 Example 5 43.2 Comparative Example 1 29.1

[0067] It can be seen from the table that the grouting sealing material prepared by the present invention has good mechanical properties.

Claims

1. A grouting sealing material, characterized in that: The grouting and sealing material is composed of the following components by weight: 100 parts of cement, 2-10 parts of waterborne epoxy resin, 5-15 parts of bentonite, 2-6 parts of terminal silane hyperbranched polyamide, 1-3 parts of defoamer, 15-25 parts of expansion agent, 0.1-0.5 parts of terminal silane polysulfonate hyperbranched polyamide, and 30-50 parts of deionized water; The preparation method of the grouting sealing material is as follows: Add cement, waterborne epoxy resin, bentonite, and terminal silane hyperbranched polyamide to deionized water, stir and mix for 5-10 minutes, then add defoamer, expansion agent, and terminal silane polysulfonate hyperbranched polyamide, and continue stirring for 5-10 minutes to obtain a grouting sealing material; The preparation method of the silane-terminated hyperbranched polyamide is: (1) Under nitrogen protection, pyromellitic anhydride and bis(2-chloroethyl)amine were added to N,N-dimethylacetamide solvent, stirred and dissolved, and reacted at room temperature for 3-5 hours. After the reaction was completed, toluene was precipitated and rotary evaporated to obtain intermediate 1; (2) The intermediate product 1 and aminopropyltriethoxysilane are added to N,N-dimethylacetamide solvent, stirred and dispersed, and the pH is adjusted to 7-9 with saturated sodium carbonate. The reaction is carried out at 40-55° C. for 6-12 hours. After the reaction is completed, the reaction is filtered and the solvent is evaporated to obtain terminal silane hyperbranched polyamide.

2. The grouting sealing material according to claim 1, characterized in that: The defoaming agent is P803 defoaming agent, and the swelling agent is UEA swelling agent.

3. The grouting sealing material according to claim 1, characterized in that: In the above (1), the molar ratio of pyromellitic anhydride to bis(2-chloroethyl)amine is 1:4.2-5.

4. The grouting sealing material according to claim 1, characterized in that: In the above (2), the molar ratio of the intermediate product 1 to aminopropyltriethoxysilane is 1:7.8-8.

4.

5. The grouting sealing material according to claim 1, characterized in that: The preparation method of the terminal silane polysulfonate hyperbranched polyamide is: Add terminal silane hyperbranched polyamide and 1,3-propane sultone into methanol solvent, stir and mix evenly, heat to 60-70°C, react for 24-48 hours, and after the reaction, add sodium carbonate, continue stirring for 1-3 hours, filter, distill under reduced pressure, and dry to obtain terminal silane polysulfonate hyperbranched polyamide.

6. The grouting and sealing material according to claim 5, characterized in that: The molar ratio of the terminal silane hyperbranched polyamide, 1,3-propane sultone and sodium carbonate is 1:8.5-10:8-8.5.

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