Polyurethane grouting material, preparation method and application thereof

Abstract

The present invention relates to the technical field of grouting materials, and discloses a polyurethane type grouting material and a preparation method and application thereof, which is composed of component A and component B; component A includes 86-92 parts by weight of biscardanol polyether polyol, 1.3-2 parts by weight of water, 0.25-0.3 parts by weight of dibutyltin dilaurate, 5-8 parts by weight of triethanolamine, and 2-3 parts by weight of foam stabilizer; component B is 25-38 parts by weight of polymethylene polyphenyl polyisocyanate. The present invention uses biscardanol polyether polyol as a polyol component, which contains rigid terphenyl, can improve the modulus and strength of the polyether soft segment, and it contains a biscardanol alkyl long chain, can be physically crosslinked by hydrophobic association, improves the crosslinking degree and cohesion of the polyurethane molecular chain, and significantly improves the compressive strength and tensile strength of the polyurethane grouting material.

Description

Technical Field

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

[0002] In recent years, my country's infrastructure and construction industries have developed rapidly. However, with the increase in service life, building facilities such as subway tunnels and building basements have problems such as cracking and leakage. Long-term water leakage will cause structural damage to building facilities and pose many safety hazards. The use of chemical grouting repair method is a common construction technology to solve the problem of building leakage. Among them, polyurethane grouting material has the advantages of wide application range and excellent anti-corrosion performance, and is the most widely used. Therefore, it is necessary to develop high-performance polyurethane grouting material.

[0003] Cashew nut shell liquid is an unsaturated amphoteric bio-grease, cheap and easy to obtain, green and pollution-free. The cardanol mainly contained is a natural biomass phenol with unique long-chain alkanes. In recent years, the development and utilization of cardanol has been a research hotspot. Using cardanol polyol as a chain extender for polyurethane, polyurethane with excellent performance can be obtained, which has good practical applications in coatings and grouting materials. Chinese patent CN103073689B discloses a preparation method of cashew nut shell oil-modified phenolic resin and cashew nut shell oil polyether polyol prepared therefrom, using cashew nut shell oil, acidic catalyst, coupling agent, alkaline catalyst, epoxy compound, etc. as raw materials to obtain cashew nut shell oil polyether polyol, which improves the alkali resistance and mechanical properties of polyurethane coatings. However, the polyurethane material does not show good heat resistance and other properties. The present invention uses bis-cardanol polyether polyol as a polyol component, which can improve the mechanical properties and heat resistance of polyurethane type grouting materials, and can meet the construction and application of grouting materials under complex environments such as high temperature. Summary of the invention

[0004] Technical problem solved: In view of the deficiencies in the prior art, the present invention solves the problems of low strength, poor mechanical properties and poor heat resistance of polyurethane grouting materials.

[0005] Technical solution: The polyurethane grouting material consists of component A and component B;

[0006] Component A includes 86-92 parts by weight of biscardanol polyether polyol, 1.3-2 parts by weight of water, 0.25-0.3 parts by weight of dibutyltin dilaurate, 5-8 parts by weight of triethanolamine, and 2-3 parts by weight of foam stabilizer SZ-1718;

[0007] Component B is 25-38 parts by weight of polymethylene polyphenyl polyisocyanate;

[0008] The preparation method of biscardanol polyether polyol is as follows: add 2,5-diphenolyl terephthalic acid cardanol ester and potassium hydroxide into a reaction kettle, introduce nitrogen, add ethylene oxide, heat to the reaction temperature, cool after the reaction, add distilled water and stir to mix, add phosphoric acid to neutralize, then add activated carbon for adsorption and decolorization, dry and remove water to obtain biscardanol polyether polyol;

[0009] The structural formula of biscardanol polyether polyol is: n=any integer value from 0 to 3.

[0010] Preferably, the reaction temperature is such that the molar ratio of 2,5-diphenyl terephthalate to ethylene oxide is 1:(30-50).

[0011] Preferably, the reaction temperature is 110-120° C. and the reaction time is 2-3 h.

[0012] Preferably, the pressure in the reactor is controlled to be 0.25-0.4 MPa during the reaction.

[0013] Preferably, the preparation method of 2,5-diphenolyl terephthalate cardanol ester is:

[0014] (1) Add toluene, cardanol, 2,5-dibromoterephthalic acid and p-toluenesulfonic acid in a molar ratio of (2.2-2.6):1:(0.16-0.24) to a reaction flask, introduce nitrogen, raise the temperature to 75-90° C., react for 12-18 hours, and distill under reduced pressure after the reaction. Separate by silica gel column chromatography, and use a solution with a volume ratio of petroleum ether:ethyl acetate = 9:1 as an eluent to obtain 2,5-dibromoterephthalic acid cardanol ester.

[0015] (2) Add 1,4-dioxane or N,N-dimethylformamide solvent, 2,5-dibromoterephthalic acid cardanol ester, 4-hydroxyphenylboronic acid pinacol ester, tetrakis(triphenylphosphine)palladium, potassium carbonate, and water to a reaction flask in a molar ratio of 1:(2-2.2):(0.08-0.11):(3.2-3.8), heat to 85-100° C., stir for reaction for 48-60 hours, add distilled water and ethyl acetate, extract and distill the organic layer under reduced pressure, separate by silica gel column chromatography, and use a solution with a volume ratio of petroleum ether:ethyl acetate = 6:1 as an eluent to obtain 2,5-diphenolyl terephthalic acid cardanol ester.

[0016] Preferably, the preparation method of the polyurethane grouting material is as follows: bis-cardanol polyether polyol, water, dibutyltin dilaurate, triethanolamine, and foam stabilizer SZ-1718 are mixed to obtain component A, and then component B is added, stirred quickly and put into a mold for foaming, and then matured at 50-60°C for 24-48h to obtain a polyurethane grouting material.

[0017] Preferably, the polyurethane grouting material is used in waterproofing and plugging leaks in construction projects.

[0018] Technical effect: The present invention conducts an esterification reaction on cardanol and 2,5-dibromoterephthalic acid, and then conducts a coupling reaction with 4-hydroxyphenylboronic acid pinacol ester to obtain a novel cardanol polyether polyol; and then uses polymethylene polyphenyl polyisocyanate, foam stabilizer, etc. as raw materials to conduct foaming and curing to obtain a polyurethane grouting material. The cardanol polyether polyol contains two hydrophilic polyether segments, which can improve the hydrophilicity of polyurethane, and has a high foaming rate and water expansion rate, which can well meet the practical application in grouting materials.

[0019] The biscardanol polyether polyol of the present invention is used as a polyol component, and it contains rigid terphenyl, which can improve the modulus and strength of the polyether soft segment, and it contains a biscardanol alkyl long chain, which can be physically cross-linked through hydrophobic association, improve the cross-linking degree and cohesion of the polyurethane molecular chain, thereby significantly improving the compressive strength and tensile strength of the polyurethane grouting material. At the same time, the terphenyl contained in the biscardanol polyether polyol has a very high thermal stability, and is introduced into the polyurethane molecular chain to increase the thermal decomposition temperature of the grouting material. The construction and application of the grouting material under complex environments such as high temperature can be met. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 The invention is a reaction route for preparing 2,5-diphenolyl terephthalate cardanol ester.

[0021] Figure 2 This is a reaction route for preparing biscardanol polyether polyol. DETAILED DESCRIPTION

[0022] Prepare cardanol polyol according to the method of the journal "Thermosetting Resins", Vol. 38, No. 1, January 2023, "Study on Cardanol Flame Retardant Polyurethane Foam Prepared by Different Isocyanates". Add 35.7g of cardanol glycidyl ether and 10.5g of diethanolamine to the reaction bottle, stir and react at 70°C for 8h, cool, and obtain cardanol polyol with the structural formula

[0023] Example 1

[0024] (1) Add 60 mL of toluene, 44 mmol of cardanol, 20 mmol of 2,5-dibromoterephthalic acid and 3.2 mmol of p-toluenesulfonic acid into a reaction flask, introduce nitrogen, heat to 75° C., react for 18 h, and distill under reduced pressure after the reaction. Separate by silica gel column chromatography, using a solution with a volume ratio of petroleum ether: ethyl acetate = 9:1 as an eluent to obtain 2,5-dibromoterephthalic acid cardanol ester.

[0025] (2) Add 80 mL of N,N-dimethylformamide solvent, 5 mmol of 2,5-dibromoterephthalic acid cardanol ester, 11 mmol of 4-hydroxyphenylboronic acid pinacol ester, 0.4 mmol of tetrakis(triphenylphosphine)palladium, 16 mmol of potassium carbonate, and 6 mL of water to the reaction bottle, heat to 100 ° C, stir and react for 48 hours, add distilled water and ethyl acetate, extract and distill the organic layer under reduced pressure, perform silica gel column chromatography separation, and use a solution with a volume ratio of petroleum ether: ethyl acetate = 6:1 as an eluent to obtain 2,5-diphenolyl terephthalic acid cardanol ester.

[0026] (3) Add 5 mmol 2,5-diphenyl terephthalate cardanol ester and 10.2 mg potassium hydroxide to the reactor, introduce nitrogen, add 150 mmol ethylene oxide, raise the temperature to 110° C., control the pressure in the reactor to 0.4 MPa, react for 2 h, cool, add distilled water and stir to mix, add phosphoric acid to neutralize, then add activated carbon for adsorption and decolorization, dry and remove water to obtain cardanol polyether polyol.

[0027] (4) 86 g of dicardanol polyether polyol, 1.3 g of water, 0.3 g of dibutyltin dilaurate, 8 g of triethanolamine, and 2.5 g of foam stabilizer SZ-1718 were mixed to obtain component A, and then 31 g of polymethylene polyphenyl polyisocyanate was added to component B. The mixture was quickly stirred and placed into a mold for foaming, and then aged at 60° C. for 36 hours to obtain a polyurethane grouting material.

[0028] Example 2

[0029] (1) Add 80 mL of toluene, 56 mmol of cardanol, 20 mmol of 2,5-dibromoterephthalic acid and 4.8 mmol of p-toluenesulfonic acid into a reaction flask, introduce nitrogen, heat to 90° C., react for 12 h, and distill under reduced pressure after the reaction. Separate by silica gel column chromatography, using a solution with a volume ratio of petroleum ether: ethyl acetate = 9:1 as an eluent to obtain 2,5-dibromoterephthalic acid cardanol ester.

[0030] (2) Add 50 mL of N,N-dimethylformamide solvent, 5 mmol of 2,5-dibromoterephthalic acid cardanol ester, 10 mmol of 4-hydroxyphenylboronic acid pinacol ester, 0.55 mmol of tetrakis(triphenylphosphine)palladium, 19 mmol of potassium carbonate, and 8 mL of water to a reaction flask, heat to 85° C., stir and react for 60 hours, add distilled water and ethyl acetate, extract and distill the organic layer under reduced pressure, perform silica gel column chromatography separation, and use a solution with a volume ratio of petroleum ether: ethyl acetate = 6:1 as an eluent to obtain 2,5-diphenolylterephthalic acid cardanol ester.

[0031] (3) Add 5 mmol 2,5-diphenyl terephthalate cardanol ester and 11.8 mg potassium hydroxide to a reactor, introduce nitrogen, add 200 mmol ethylene oxide, raise the temperature to 110° C., control the pressure in the reactor to 0.3 MPa, react for 2 h, cool, add distilled water and stir to mix, add phosphoric acid to neutralize, then add activated carbon for adsorption and decolorization, dry and remove water to obtain cardanol polyether polyol.

[0032] (4) 92 g of dicardanol polyether polyol, 1.6 g of water, 0.25 g of dibutyltin dilaurate, 5 g of triethanolamine, and 3 g of foam stabilizer SZ-1718 were mixed to obtain component A, and then 25 g of component B, polymethylene polyphenyl polyisocyanate, were added, stirred rapidly and poured into a mold for foaming, and then aged at 50° C. for 48 h to obtain a polyurethane grouting material.

[0033] Example 3

[0034] (1) Prepare 2,5-diphenyl terephthalate according to the method of Example 2.

[0035] (2) Add 5 mmol 2,5-diphenyl terephthalate cardanol ester and 11.8 mg potassium hydroxide into a reactor, introduce nitrogen, add 200 mmol ethylene oxide, raise the temperature to 120° C., control the pressure in the reactor to 0.25 MPa, react for 3 h, cool, add distilled water and stir to mix, add phosphoric acid to neutralize, then add activated carbon for adsorption and decolorization, dry and remove water to obtain cardanol polyether polyol.

[0036] (3) 87 g of dicardanol polyether polyol, 1.4 g of water, 0.3 g of dibutyltin dilaurate, 8 g of triethanolamine, and 2 g of foam stabilizer SZ-1718 were mixed to obtain component A, and then 38 g of component B, polymethylene polyphenyl polyisocyanate, were added, stirred rapidly and poured into a mold for foaming, and then aged at 50° C. for 36 hours to obtain a polyurethane grouting material.

[0037] Example 4

[0038] (1) Prepare 2,5-diphenyl terephthalate according to the method of Example 2.

[0039] (2) Add 5 mmol 2,5-diphenyl terephthalate cardanol ester and 13.8 mg potassium hydroxide into a reactor, introduce nitrogen, add 250 mmol ethylene oxide, raise the temperature to 120° C., control the pressure in the reactor to 0.3 MPa, react for 3 h, cool, add distilled water and stir to mix, add phosphoric acid to neutralize, then add activated carbon for adsorption and decolorization, dry and remove water to obtain cardanol polyether polyol.

[0040] (3) 88 g of dicardanol polyether polyol, 2 g of water, 0.3 g of dibutyltin dilaurate, 6.3 g of triethanolamine, and 3 g of foam stabilizer SZ-1718 were mixed to obtain component A, and then 34 g of component B, polymethylene polyphenyl polyisocyanate, was added, stirred rapidly and poured into a mold for foaming, and then aged at 60° C. for 24 h to obtain a polyurethane grouting material.

[0041] Comparative Example 1

[0042] 86g of polyether polyol N330, 1.3g of water, 0.3g of dibutyltin dilaurate, 8g of triethanolamine, and 2.5g of foam stabilizer SZ-1718 were mixed to obtain component A, and then 31g of polymethylene polyphenyl polyisocyanate, component B, were added, stirred rapidly and put into a mold for foaming, and then aged at 60°C for 36h to obtain a polyurethane grouting material.

[0043] Comparative Example 2

[0044] 86g of cardanol polyol 1.3g water, 0.3g dibutyltin dilaurate, 8g triethanolamine, and 2.5g foam stabilizer SZ-1718 were mixed to obtain component A, and then 31g polymethylene polyphenyl polyisocyanate component B was added, and the mixture was quickly stirred and put into a mold for foaming, and then aged at 60°C for 36h to obtain a polyurethane grouting material.

[0045] The hydrophilicity, foaming rate and water expansion rate of polyurethane grouting materials were tested according to the method of JC / T 2041-2020. The test results are shown in the following table:

[0046] Table 1 Hydrophilicity test of polyurethane grouting materials

[0047] Hydrophilicity Foaming rate (times) Water expansion rate (%) Example 1 Milky white, uniform and particle-free 21.8 764.1 Example 2 Milky white, uniform and particle-free 39.5 1203.5 Example 3 Milky white, uniform and particle-free 23.6 826.4 Example 4 Milky white, uniform and particle-free 31.1 1007.8 Comparative Example 1 Milky white, uniform and particle-free 25.9 894.0 Comparative Example 2 There are obvious floccules 4.6 196.7

[0048] After testing Examples 1-4 using biscardanol polyether polyol, polymethylene polyphenyl polyisocyanate, etc. as raw materials, the obtained polyurethane grouting material has good hydrophilicity. Thanks to the biscardanol polyether polyol containing two hydrophilic polyether segments, the hydrophilicity of polyurethane can be improved, and the foaming rate and water expansion rate are high, which can well meet the practical application in grouting materials.

[0049] In Comparative Example 1, polyether polyol N330 is used as the polyol component, and the obtained polyurethane grouting material also has good hydrophilicity, high foaming rate and water expansion rate.

[0050] In Comparative Example 2, cardanol-based polyol is used as the polyol, which does not contain a hydrophilic polyether segment. The obtained polyurethane grouting material has poor hydrophilicity, and the polyurethane does not have a flexible soft segment, and is difficult to foam to form a stable foam material. The foaming rate and water expansion rate are very low, which cannot meet the actual application requirements in grouting materials.

[0051] The compressive strength of the grouting material is tested according to the method of JG / T316-2011; the tensile strength of the grouting material is tested according to the method of JG / T316-2011.

[0052] The thermal properties of the grouting material were tested using a thermogravimetric analyzer in a nitrogen atmosphere with a heating rate of 5°C / min and a test temperature of 25-700°C. (5％) The temperature at which the mass loss is 5%. The test results are shown in the following table.

[0053] Table 2 Performance test of polyurethane grouting materials

[0054] Compressive strength(MPa) Tensile strength(MPa) <![CDATA[T (5％) (℃)]]> Example 1 26.5 1.47 326.7 Example 2 20.8 0.94 315.6 Example 3 24.4 1.16 316.7 Example 4 21.6 1.09 309.4 Comparative Example 1 12.3 0.70 302.5

[0055] In Examples 1-4, biscardanol polyether polyol is used as the polyol component, which contains rigid terphenyl The modulus and strength of the polyether soft segment can be improved, and the long chain of biscardanol alkyl can be physically cross-linked through hydrophobic association, thereby improving the cross-linking degree and cohesion of the polyurethane molecular chain, thereby significantly improving the compressive strength and tensile strength of the polyurethane grouting material, which is much higher than the grouting material of Comparative Example 1. At the same time, the terphenyl contained in the biscardanol polyether polyol has high thermal stability, and when introduced into the polyurethane molecular chain, the thermal decomposition temperature of the grouting material can be increased. It can meet the construction and application of the grouting material in a high temperature environment.

Claims

1. Polyurethane grouting material, characterized in that: The polyurethane grouting material consists of component A and component B; Component A comprises 86-92 parts by weight of biscardanol polyether polyol, 1.3-2 parts by weight of water, 0.25-0.3 parts by weight of dibutyltin dilaurate, 5-8 parts by weight of triethanolamine, and 2-3 parts by weight of a foam stabilizer; Component B is 25-38 parts by weight of polymethylene polyphenyl polyisocyanate; The preparation method of the biscardanol polyether polyol is as follows: add 2,5-diphenolyl terephthalic acid cardanol ester and potassium hydroxide into a reaction kettle, introduce nitrogen, add ethylene oxide, heat to the reaction temperature, cool after the reaction, add distilled water and stir to mix, add phosphoric acid to neutralize, then add activated carbon for adsorption and decolorization, dry and remove water to obtain the biscardanol polyether polyol; The structural formula of the 2,5-diphenolyl terephthalate cardanol ester is: , n=any integer value from 0 to 3.

2. The polyurethane grouting material according to claim 1, characterized in that: The molar ratio of the 2,5-diphenolyl terephthalate cardanol ester to ethylene oxide is 1:(30-50).

3. The polyurethane grouting material according to claim 1, characterized in that: The reaction temperature is 110-120° C., and the reaction time is 2-3 hours.

4. The polyurethane grouting material according to claim 1, characterized in that: During the reaction, the pressure in the reactor was controlled to be 0.25-0.4 MPa.

5. The polyurethane grouting material according to claim 1, characterized in that: The preparation method of the 2,5-diphenolyl terephthalate cardanol ester is: (1) Add toluene, cardanol, 2,5-dibromoterephthalic acid and p-toluenesulfonic acid in a molar ratio of (2.2-2.6):1:(0.16-0.24) into a reaction flask, introduce nitrogen, raise the temperature to 75-90°C, react for 12-18 hours, perform vacuum distillation after the reaction, separate by silica gel column chromatography, and obtain 2,5-dibromoterephthalic acid cardanol ester; (2) Add a solvent, 2,5-dibromoterephthalic acid cardanol ester, 4-hydroxyphenylboronic acid pinacol ester, tetrakis(triphenylphosphine)palladium, potassium carbonate and water to a reaction flask, raise the temperature to the reaction temperature, stir the reaction, add distilled water and ethyl acetate, extract, distill the organic layer under reduced pressure, and separate by silica gel column chromatography to obtain 2,5-diphenolylterephthalic acid cardanol ester.

6. The polyurethane grouting material according to claim 5, characterized in that: The solvent in (2) is 1,4-dioxane or N,N-dimethylformamide.

7. The polyurethane grouting material according to claim 5, characterized in that: The molar ratio of 2,5-dibromoterephthalic acid cardanol ester, 4-hydroxyphenylboronic acid pinacol ester, tetrakis(triphenylphosphine)palladium and potassium carbonate in (2) is 1:(2-2.2):(0.08-0.11):(3.2-3.8).

8. The polyurethane grouting material according to claim 5, characterized in that: The reaction temperature in (2) is 85-100°C and the reaction time is 48-60h.

9. A method for preparing the polyurethane grouting material according to any one of claims 1 to 8, characterized in that: Mix biscardanol polyether polyol, water, dibutyltin dilaurate, triethanolamine and foam stabilizer to obtain component A, then add component B, stir quickly and put into a mold for foaming, and then mature at 50-60°C for 24-48h to obtain a polyurethane grouting material.

10. Use of the polyurethane grouting material obtained by the preparation method as claimed in claim 9 in waterproofing and plugging of construction projects.

Images