High-toughness high-molecular flexible auxiliary anti-seepage protective material and preparation method thereof

Abstract

The invention relates to the technical field of anti-seepage protective materials, in particular to a high-toughness high-molecular flexible auxiliary anti-seepage protective material and a preparation method thereof, and the high-toughness high-molecular flexible auxiliary anti-seepage protective material comprises a component A and a component B, the component A at least comprises the following preparation raw materials: first polyol, a chain extender, diisocyanate and an anti-aging agent, the mass ratio of the diisocyanate in the component A is 22-35%, and the mass ratio of the anti-aging agent in the component A is 0.1-1%; the first polyhydric alcohol is prepared from poly (neopentyl glycol adipate)-1, 6-hexanediol ester glycol, hydrogenated castor oil polyether polyol, polytetrahydrofuran glycol and polyfunctional polyether polyol, and the second polyhydric alcohol is prepared from poly (neopentyl glycol adipate)-1, 6-hexanediol ester glycol, hydrogenated castor oil polyether polyol, polytetrahydrofuran glycol and polyfunctional polyether polyol; the chain extender is prepared from dipropylene glycol and methyl propylene glycol; the component B is prepared from the following raw materials: second polyol, a plasticizer, a filler and an amine catalyst, and is subsequently coated on the surfaces of base materials such as asphalt concrete and concrete to isolate a bottom structure from the external environment, so that the effects of isolation, seepage prevention, protection, insulation, flame retardance and the like are achieved.

Description

Technical Field

[0001] The present invention relates to the technical field of anti-seepage protection materials, in particular to a high-toughness polymer flexible auxiliary anti-seepage protection material and a preparation method thereof. Background Art

[0002] There are great differences in climate between the east and west, and between the north and south of my country. In severely cold regions, the extremely low temperature in winter can reach around -55°C. In these severely cold regions, the currently available thermosetting and thermoplastic anti-seepage materials will lose their toughness and become brittle below -30°C. When subjected to large external forces, they will crack, resulting in damage to the waterproof layer, and cannot be used as anti-seepage protective materials in severely cold regions. Therefore, it is necessary to find ways to reduce the brittleness of anti-seepage materials at low temperatures, increase their toughness, and improve their bearing strength. A Chinese patent application (publication number CN119118567A) discloses a dam anti-seepage material suitable for extreme environments and its application method. The material uses a combination of self-expanding particles, epoxy resin, water-based polyurethane curing agent and composite agent. By applying a sticky film on the surface of the self-expanding particles, combined with leakage detection and a layered laying method of composite hydrated fossil materials, the adhesion and stability of the material are enhanced, and the anti-seepage performance is improved. A Chinese patent (authorization publication number CN117534421B) discloses an anti-seepage material, a preparation method, and its application in dam construction. The anti-seepage material is composed of a hydraulic inorganic gel material and specific additives, including a hydraulic inorganic gel material (such as cement or recycled cement) and additives (bentonite, modified basalt fiber, and modified polyurethane). The anti-seepage performance of the material is improved through modification.

[0003] However, a pumped-storage power station in Heilongjiang Province, located in the northernmost part of Northeast my country, boasts the world's coldest winter temperatures. Asphalt concrete is proposed as the primary anti-seepage material for its upper reservoir basin. To prevent cracking in the asphalt concrete at temperatures below -50°C, a polymer coating is proposed for use as a secondary anti-seepage protection. In addition to possessing the properties of conventional waterproofing materials, this polymer must also maintain a strong bond with the asphalt concrete at temperatures as low as -55°C, possess high toughness and resist brittle failure, and be able to absorb energy generated by external forces. This ensures both anti-seepage requirements for high water heads (under 100 meters) and protection for the underlying asphalt concrete structure. Currently, no material on the market meets these requirements. Summary of the Invention

[0004] In order to solve the above problems, the present invention provides a high-toughness polymer flexible auxiliary anti-seepage protective material, which is subsequently coated on the surface of a substrate such as concrete and asphalt concrete. After curing, it is firmly bonded to the substrate to isolate the bottom structure from the external environment, and plays the role of isolation, anti-seepage, protection, insulation, and flame retardancy.

[0005] On one hand, the present invention provides a high-toughness polymer flexible auxiliary anti-seepage protective material, comprising a component A and a component B; the raw materials for preparing the component A include at least: a first polyol, a chain extender, a diisocyanate, and an anti-aging agent, the mass proportion of the diisocyanate in the component A is 22-35%, and the mass proportion of the anti-aging agent is 0.1-1%; the first polyol includes at least: poly (neopentyl adipate glycol-1,6-hexanediol ester diol), hydrogenated castor oil polyether polyol, polytetrahydrofuran diol, and a multifunctional polyether polyol; the chain extender includes at least: dipropylene glycol and methyl propylene glycol; the raw materials for preparing the component B include at least: a second polyol, a plasticizer, a filler, and an amine catalyst.

[0006] In one embodiment, the raw materials for preparing component A include at least 11-15 parts by weight of polyneopentyl adipate-1,6-hexanediol ester diol, 15-18 parts by weight of hydrogenated castor oil polyether polyol, 10-20 parts by weight of polytetramethylene glycol, 15-20 parts by weight of multifunctional polyether polyol, 4-8 parts by weight of dipropylene glycol, 5-10 parts by weight of methyl propylene glycol, 24-30 parts by weight of diisocyanate, and 0.15-0.58 parts by weight of anti-aging agent.

[0007] In one embodiment, the raw materials for preparing component A include at least 12-13 parts by weight of polyneopentyl adipate-1,6-hexanediol ester diol, 15-18 parts of hydrogenated castor oil polyether polyol, 12-16 parts of polytetramethylene glycol, 15-20 parts of multifunctional polyether polyol, 5-7 parts of dipropylene glycol, 5.63-9.42 parts of methyl propylene glycol, 24-30 parts of diisocyanate, and 0.15-0.58 parts of anti-aging agent.

[0008] In one embodiment, the functionality of the multifunctional polyether polyol is 3-4.

[0009] In one embodiment, the number average molecular weight of the multifunctional polyether polyol is 4000-6000.

[0010] In one embodiment, the number average molecular weight of the multifunctional polyether polyol is 5,000.

[0011] The present invention adopts a polyol combination including polyneopentyl adipate-1,6-hexanediol ester diol, hydrogenated castor oil polyether polyol, polytetramethylene glycol, and multifunctional polyether polyol, which reacts with the diisocyanate in the system to generate a soft and hard segment structure with a longer molecular chain. The provided product has excellent auxiliary anti-seepage protection effect after being used on the asphalt concrete surface. It still maintains a strong bond with the asphalt concrete at a low temperature of -55°C, has high toughness, and does not suffer brittle failure. The material itself can absorb the energy generated by external forces, meeting the anti-seepage requirements of higher water heads (below 100 meters) and the protection requirements for the lower asphalt concrete structure.

[0012] Furthermore, the present invention simultaneously introduces dipropylene glycol and methyl propylene glycol as chain extenders and controls the addition amounts of the two, thereby further improving the flexibility and corrosion resistance of the polyurethane product while balancing the strength of the product.

[0013] In one embodiment, the diisocyanate includes at least xylylene diisocyanate and dicyclohexylmethane diisocyanate.

[0014] In one embodiment, the mass ratio of xylylene diisocyanate to dicyclohexylmethane diisocyanate is (12-15):(12-15).

[0015] In one embodiment, the anti-aging agent includes an antioxidant and a UV absorber.

[0016] In one embodiment, the antioxidant is selected from at least one of antioxidant 245, antioxidant 1790, antioxidant 1010, antioxidant 1076, antioxidant 264 (BHT), antioxidant 1135R, antioxidant 168, triphenyl phosphite (TPP), tris(nonylphenyl) phosphite (TNPP) or diphenyl isodecyl phosphite (DPDP).

[0017] In one embodiment, the antioxidant is antioxidant 1010.

[0018] In one embodiment, the ultraviolet absorber is selected from at least one of UV-327, UV-9, UV-21 or UV-326.

[0019] In one embodiment, the ultraviolet absorber is UV-327.

[0020] Furthermore, the present invention optimizes the diisocyanate in component A to be a combination of xylylene diisocyanate and dicyclohexylmethane diisocyanate, further controls the addition amounts of diisocyanate, polyol, and chain extender in the system, and under the combined action of antioxidant 1010 and UV-327, balances the curing speed, strength, and toughness of the product while providing the product with excellent yellowing resistance, UV aging resistance, and light aging resistance, thereby better meeting practical application requirements.

[0021] In one embodiment, the mass ratio of component A to component B is 1:(0.5-2).

[0022] In one embodiment, the raw materials for preparing the second component include at least 30-45 parts of the second polyol, 23-30 parts of the plasticizer, 35-40 parts of the filler, and 3.2-5.4 parts of the amine catalyst, calculated by weight.

[0023] In one embodiment, the second polyol includes at least polyoxypropylene glycol and polyether polyol.

[0024] In one embodiment, the mass ratio of the polyoxypropylene glycol to the polyether polyol is (20-25): (10-15).

[0025] In one embodiment, the plasticizer includes at least diethylene glycol dibenzoate and dimethyl methyl phosphate.

[0026] In one embodiment, the mass ratio of diethylene glycol dibenzoate to dimethyl methyl phosphate is (18-22): (5-8).

[0027] In one embodiment, the filler is selected from at least one of light calcium carbonate, heavy calcium carbonate, barium sulfate, talc or montmorillonite.

[0028] In one embodiment, the amine catalyst includes at least triethanolamine and di-n-octylamine.

[0029] In one embodiment, the mass ratio of triethanolamine to di-n-octylamine is (3-5):(0.2-0.4).

[0030] Furthermore, the present invention optimizes the second component to include polyoxypropylene glycol and polyether polyol, thereby further increasing the polyurethane molecular chain and increasing the strength while further increasing the polyurethane three-dimensional network structure, thereby improving the elastic recovery rate of the polyurethane product. The unreacted portion of the polyether polyol can be used as a plasticizer to increase the plasticity of the polyurethane material, improve the elongation at break, and ensure the comprehensive performance of the polyurethane product.

[0031] In addition, the present invention further improves the low-temperature resistance, toughness and flame retardancy of the product by introducing diethylene glycol dibenzoate and dimethyl methyl phosphate, so that the provided product can be used for auxiliary anti-seepage protection of the upper reservoir basin of pumped storage power stations in cold regions, and can also be widely used in various projects such as water conservancy, municipal administration, and transportation.

[0032] On the other hand, the present invention provides a method for preparing a high-toughness polymer flexible auxiliary anti-seepage protective material, which comprises at least the following steps: stirring and mixing the raw materials of component A to obtain component A, and stirring and mixing the raw materials of component B to obtain component B; when using, stirring and mixing component A and component B to obtain the product.

[0033] In one embodiment, the preparation method of the component A comprises at least the following steps: adding poly (neopentyl adipate glycol-1,6-hexanediol) ester diol, hydrogenated castor oil polyether polyol, polytetrahydrofuran diol, polyether polyol, dipropylene glycol and methyl propylene glycol to a reaction vessel, heating to 110-120° C. under stirring, controlling the vacuum degree to 0.095-0.1 MPa (gauge pressure negative pressure), and maintaining at 110-120° C. for 1.5-3 hours; cooling to 70-90° C., adding xylene diisocyanate and dicyclohexylmethane diisocyanate dropwise in sequence, and stirring under vacuum for 3-5 hours; lowering the temperature to 35-45° C., adding an ultraviolet absorber and an antioxidant, and stirring under vacuum for 20-40 minutes before discharging to obtain a polyurethane prepolymer (i.e., component A), which is placed in a sealed container under nitrogen protection for later use.

[0034] In one embodiment, the preparation method of the component B comprises at least the following steps: dehydrating the filler; adding the polyol, plasticizer and the dehydrated filler into a reaction vessel, controlling the vacuum degree to 0.095-0.1 MPa (gauge pressure negative pressure), heating to 120-125° C., and stirring under vacuum for 1.5-3 hours; lowering the temperature to 35-45° C., adding an amine catalyst, vacuum stirring for 0.8-1.5 hours, discharging, and placing in a sealed container under nitrogen protection for later use.

[0035] Beneficial effects

[0036] 1. The present invention provides a high-toughness polymer flexible auxiliary anti-seepage protective material, which is subsequently coated on the surface of a substrate such as concrete and asphalt concrete. After curing, it is firmly bonded to the substrate to isolate the bottom structure from the external environment, and plays the role of isolation, anti-seepage, protection, insulation, and flame retardancy.

[0037] 2. The present invention adopts a polyol combination including polyneopentyl adipate-1,6-hexanediol ester diol, hydrogenated castor oil polyether polyol, polytetramethylene glycol, and multifunctional polyether polyol, which reacts with the diisocyanate in the system to generate a soft and hard segment structure with a longer molecular chain. The provided product has excellent auxiliary anti-seepage protection effect after being used on the asphalt concrete surface. It still maintains a strong bond with the asphalt concrete at a low temperature of -55°C, has high toughness, and does not suffer brittle failure. The material itself can absorb the energy generated by external forces, meeting the anti-seepage requirements of higher water heads (below 100 meters) and the protection requirements for the lower asphalt concrete structure.

[0038] 3. The present invention simultaneously introduces dipropylene glycol and methyl propylene glycol as chain extenders and controls the addition amounts of the two to further improve the flexibility and corrosion resistance of the polyurethane product while balancing the strength of the product.

[0039] 4. The present invention optimizes the diisocyanate in component A to be a combination of xylylene diisocyanate and dicyclohexylmethane diisocyanate, further controls the addition amounts of diisocyanate, polyol, and chain extender in the system, and under the combined action of antioxidant 1010 and UV-327, balances the curing speed, strength, and toughness of the product while providing the product with excellent yellowing resistance, UV aging resistance, and light aging resistance, thereby better meeting practical application requirements.

[0040] 5. The present invention optimizes component B to include polyoxypropylene glycol and polyether polyol, thereby further increasing the polyurethane molecular chain and increasing the strength while further increasing the polyurethane three-dimensional network structure, thereby improving the elastic recovery rate of the polyurethane product. The unreacted part of the polyether polyol can be used as a plasticizer to increase the plasticity of the polyurethane material, improve the elongation at break, and ensure the comprehensive performance of the polyurethane product.

[0041] 6. The present invention further improves the low-temperature resistance, toughness and flame retardancy of the product by introducing diethylene glycol dibenzoate and dimethyl methyl phosphate, so that the provided product can be used for auxiliary anti-seepage protection of the upper reservoir basin of pumped storage power stations in cold areas, and can also be widely used in various projects such as water conservancy, municipal administration, and transportation. DETAILED DESCRIPTION

[0042] Examples 1-3, Comparative Examples 1-3

[0043] On the one hand, Examples 1-3 and Comparative Examples 1-3 of the present invention provide a high-toughness polymer flexible auxiliary anti-seepage protective material. The formula is shown in Table 1 in parts by weight.

[0044] Table 1

[0045]

[0046]

[0047] On the other hand, Examples 1-3 and Comparative Examples 1-3 of the present invention provide a method for preparing a high-toughness polymer flexible auxiliary anti-seepage protective material, comprising the following steps:

[0048] (1) Add poly (neopentyl adipate glycol-1,6-hexanediol) ester diol, hydrogenated castor oil polyether polyol, polytetrahydrofuran diol, polyether polyol, dipropylene glycol and methyl propylene glycol into a reaction vessel, heat to 120°C under stirring, control the vacuum degree to 0.095 MPa (gauge pressure negative pressure), and maintain at 120°C for 2 hours; cool to 80°C, dropwise add xylene diisocyanate and dicyclohexylmethane diisocyanate in sequence, and stir under vacuum for 4 hours; cool to 40°C, add ultraviolet absorber and antioxidant, stir under vacuum for 30 minutes, and then discharge to obtain a polyurethane prepolymer (i.e., component A), which is placed in a sealed container under nitrogen protection for standby use;

[0049] (2) Dewater the filler (120°C oven, 8 hours); add the polyol, plasticizer, and dewatered filler into a reaction vessel, control the vacuum degree to 0.095 MPa (gauge pressure negative pressure), heat to 120°C, and stir under vacuum for 2 hours; lower the temperature to 40°C, add an amine catalyst, stir under vacuum for 1 hour, discharge, and place in a sealed container under nitrogen protection for later use;

[0050] (3) When using, stir and mix component A and component B.

[0051] Performance Testing

[0052] 1. The auxiliary anti-seepage protective materials provided in each embodiment and comparative example were coated on the surface of a substrate (the substrate was asphalt concrete) (wet film thickness was 3 mm), and the tests in Table 2 were performed with reference to the standards. The results are shown in Table 2.

[0053] Table 2

[0054]

[0055]

[0056] Analysis of the data in Table 2 shows that the products provided by Examples 1-3 of the present invention have excellent curing rate, strength, toughness, low temperature resistance, aging resistance, anti-seepage performance and thermal conductivity compared to Comparative Examples 1-3, and better meet the actual application requirements.

Claims

1. A high-toughness polymer flexible auxiliary anti-seepage protective material, characterized in that: The invention comprises a component A and a component B; the raw materials for preparing the component A at least include: a first polyol, a chain extender, a diisocyanate, and an anti-aging agent, wherein the mass proportion of the diisocyanate in the component A is 22-35%, and the mass proportion of the anti-aging agent is 0.1-1%; the first polyol at least includes: poly (neopentyl adipate-1,6-hexanediol) ester diol, hydrogenated castor oil polyether polyol, polytetramethylene glycol, and a multifunctional polyether polyol; The chain extender at least includes: dipropylene glycol, methyl propylene glycol; The raw materials for preparing the second component at least include: a second polyol, a plasticizer, a filler, and an amine catalyst.

2. The high-toughness polymer flexible auxiliary anti-seepage protective material according to claim 1, characterized in that: The raw materials for preparing the component A include at least 12-13 parts by weight of polyneopentyl adipate-1,6-hexanediol ester diol, 15-18 parts of hydrogenated castor oil polyether polyol, 12-16 parts of polytetramethylene glycol, 15-20 parts of multifunctional polyether polyol, 5-7 parts of dipropylene glycol, 5.63-9.42 parts of methyl propylene glycol, 24-30 parts of diisocyanate, and 0.15-0.58 parts of anti-aging agent.

3. The high-toughness polymer flexible auxiliary anti-seepage protective material according to claim 1, characterized in that: The diisocyanate includes at least xylylene diisocyanate and dicyclohexylmethane diisocyanate.

4. The high-toughness polymer flexible auxiliary anti-seepage protective material according to claim 1, characterized in that: The anti-aging agent includes an antioxidant and an ultraviolet absorber.

5. The high-toughness polymer flexible auxiliary anti-seepage protective material according to claim 4, characterized in that: The antioxidant is selected from at least one of antioxidant 245, antioxidant 1790, antioxidant 1010, antioxidant 1076, antioxidant 264, antioxidant 1135R, antioxidant 168, TPP, TNPP or DPDP.

6. The high-toughness polymer flexible auxiliary anti-seepage protective material according to claim 4, characterized in that: The ultraviolet absorber is selected from at least one of UV-327, UV-9, UV-21 or UV-326.

7. The high-toughness polymer flexible auxiliary anti-seepage protective material according to claim 1, characterized in that: The mass ratio of component A to component B is 1:(0.5-2).

8. The high-toughness polymer flexible auxiliary anti-seepage protective material according to claim 7, characterized in that: In parts by weight, the raw materials for preparing the second component include at least: 30-45 parts of polyol, 23-30 parts of plasticizer, 35-40 parts of filler, and 3.2-5.4 parts of amine catalyst.

9. The use of the high-toughness polymer flexible auxiliary anti-seepage protective material according to claim 8, characterized in that: The second polyol includes at least polyoxypropylene glycol and polyether polyol.

10. A method for preparing the high-toughness polymer flexible auxiliary anti-seepage protective material according to any one of claims 1 to 9, characterized in that: The method comprises at least the following steps: stirring and mixing the raw materials of component A to obtain component A, stirring and mixing the raw materials of component B to obtain component B; and stirring and mixing component A and component B to obtain the product when in use.

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