CN113429744B - Preparation method of MOFs-containing epoxy resin/polyurethane IPNs grouting material - Google Patents
Preparation method of MOFs-containing epoxy resin/polyurethane IPNs grouting material Download PDFInfo
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- CN113429744B CN113429744B CN202110832265.8A CN202110832265A CN113429744B CN 113429744 B CN113429744 B CN 113429744B CN 202110832265 A CN202110832265 A CN 202110832265A CN 113429744 B CN113429744 B CN 113429744B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks
Abstract
A preparation method of MOFs-containing epoxy resin/polyurethane IPNs grouting material belongs to the field of high polymer grouting material, and comprises the following steps: step one, uniformly mixing MOFs nano materials and epoxy resin, heating to 60-80 ℃, stirring for 30-60 min, and cooling to obtain a part of open-loop MOFs functionalized epoxy resin prepolymer serving as a component A; mixing isocyanate and polyether polyol, reacting for 3-5 h at the temperature of 60-80 ℃, and cooling to obtain a polyurethane prepolymer which is a component B; and step three, A, B is mixed, a curing agent is added into the AB mixture, the mixture is uniformly stirred, vacuumized, defoamed and cured, and the epoxy resin/polyurethane IPNs grouting material containing MOFs is obtained. The epoxy resin/polyurethane IPNs grouting material containing MOFs has excellent tensile resistance and bonding strength and also has good flame retardant property.
Description
Technical Field
The invention relates to the field of high polymer grouting materials, in particular to a preparation method of an epoxy resin/polyurethane IPNs grouting material containing MOFs.
Background
Polyurethane (PU) has the characteristics of low viscosity, controllable curing time, low toxicity, easy reaction when meeting water and the like, so that the PU can be widely applied and researched in the engineering fields of roadbed repair, dam reinforcement and the like. In recent years, polyurethane has become the most commonly used resin matrix for chemical grouting materials. Although polyurethane has many excellent properties, its use in extreme environments such as high temperature, frozen soil, etc. is limited by its high brittleness, low consolidation strength, and easy shrinkage due to water loss. The traditional polyurethane grouting material is difficult to meet the requirements of future geotechnical engineering and roadbed engineering. Therefore, the development of a novel polyurethane grouting material with good mechanical property, high consolidation strength and excellent flame retardant property is very important for the development of the building industry.
Currently, there are two main approaches to the modification of polyurethanes. The method is characterized in that the thermosetting resin and the polyurethane are physically blended to form the resin-based composite material with excellent performance. Epoxy resin has the characteristics of high chemical stability, high consolidation strength, low shrinkage rate and the like and is widely applied to the toughening research of polyurethane, but the toughening effect of the epoxy resin/polyurethane grouting material prepared by a physical blending method is not obviously improved due to compatibility. In the second method, inorganic nanoparticles such as silicon dioxide and graphene are used for toughening the polyurethane, but the inorganic nanoparticles are easy to agglomerate in a resin matrix and can seriously affect the mechanical property of the polyurethane. Aiming at the problems, the selection of proper filler has great significance for improving the performance of the epoxy resin/polyurethane composite system.
Disclosure of Invention
The invention aims to solve the problems of high brittleness and low bonding strength of polyurethane as a grouting material in the prior art, and provides a preparation method of an epoxy resin/polyurethane IPNs grouting material containing MOFs.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of epoxy resin/polyurethane IPNs grouting material containing MOFs comprises the following steps:
step one, weighing MOFs nano material and epoxy resin according to the mass ratio of 0.001: 1-0.01: 1, uniformly mixing, heating to 60-80 ℃ under the protection of nitrogen, stirring at constant temperature for 30-60 minutes, and cooling to obtain a part of ring-opened MOFs functionalized epoxy resin prepolymer serving as a component A;
step two, uniformly mixing isocyanate and polyether polyol according to the mass ratio of 1:1, reacting for 3-5 hours at the temperature of 60-80 ℃, and cooling to obtain a polyurethane prepolymer serving as a component B;
and step three, mixing A, B two components according to the mass ratio of 3: 1-5: 1 to obtain an AB mixture containing MOFs, adding a curing agent into the AB mixture containing MOFs according to the mass ratio of 1: 0.1-1: 0.5, uniformly stirring at room temperature, vacuumizing and defoaming, and curing in a vacuum drying oven at 40-100 ℃ for 5-10 hours to obtain the epoxy resin/polyurethane IPNs grouting material containing MOFs.
Furthermore, in the step one, the MOFs nano material is a coordination type compound which is formed by taking 2-amino terephthalic acid and derivatives thereof as organic chain segments and taking transition metal ions as coordination centers.
Further, in the first step, the epoxy resin includes one of bisphenol a epoxy resin E51, bisphenol a epoxy resin E44, and bisphenol F epoxy resin F51.
Further, in the second step, the isocyanate includes one of toluene diisocyanate, 4' -diphenylmethane diisocyanate, and isophorone diisocyanate.
Further, in the second step, the polyether polyol includes one of polyether polyol N204 and polyether polyol N303.
Further, in the third step, the curing agent includes one of 2-methylimidazole, 2-ethylimidazole and 2-ethyl-4-methylimidazole.
Further, in the third step, the mass ratio of the MOFs functionalized epoxy resin prepolymer to the polyurethane prepolymer is 3: 1-5: 1.
Furthermore, the mass ratio of the AB mixture containing the MOFs to the curing agent is 1: 0.1-1: 0.5.
Compared with the prior art, the invention has the beneficial effects that:
the invention adopts MOFs nano material as filler to prepare the MOFs-containing epoxy resin/polyurethane IPNs grouting material. The MOFs nano material effectively avoids the agglomeration of the MOFs nano material in a resin system due to the existence of a large amount of hydroxyl and amino, can obviously improve the compatibility between epoxy resin and polyurethane, promotes the resin system to form an IPNs structure, and obviously enhances the toughness and the bonding strength of the composite material. The MOFs-containing epoxy resin/polyurethane IPNs grouting material has excellent tensile resistance and bonding strength and good flame retardant property.
Detailed Description
The following examples are illustrative only and are not to be construed as limiting the invention.
The Metal Organic Frameworks (MOFs) are organic/inorganic nanoparticles with high chemical stability and controllable structure, can be used as a connecting agent of epoxy resin and polyurethane, effectively improve the compatibility of an epoxy resin/polyurethane composite system, and increase the Interpenetrating Polymer Networks (IPNs) of the resin composite system, so that the consolidation strength and the mechanical property of the composite system are enhanced. Furthermore, the high chemical stability of the MOFs may also improve the flame retardancy of epoxy/polyurethane composite systems. Therefore, the MOFs nano material becomes one of the keys for preparing the filling type high-performance grouting material.
Example 1
(1) Preparing MOFs nano materials: h is to be2BDC-NH2(0.816g, 4.52mmol) was dissolved in 15mL of a mixed solvent (volume ratio of N, N-dimethylformamide to anhydrous methanol: 9:1), and the mixture was added to the solutionTPOT (0.45mL, 1.5mmol) was added to the solution; after stirring at room temperature for 30 minutes, the mixture was transferred to an autoclave with a 100mL tetrafluoroethylene liner and allowed to stand in an oven at 150 ℃ for 24 hours. And filtering after natural cooling, washing the filtered yellow solid product with N, N-dimethylformamide for 24 hours, and then replacing with anhydrous methanol for 24 hours to remove the residual reactant. Finally, drying the yellow solid in a vacuum oven at 100 ℃ for 12 hours to obtain yellow powder, namely NH2-MIL-125。
(2) 300g of epoxy resin and 0.3g of NH2Adding MIL-125 into a three-neck flask with a thermometer, heating to 60 ℃ under the protection of nitrogen, stirring for 30 minutes at constant temperature, and cooling to obtain a part of ring-opened MOFs functionalized epoxy resin prepolymer which is marked as component A.
(3) 100g of toluene diisocyanate and 100g of polyether polyol (N204) react for 5 hours at the temperature of 60 ℃, and a polyurethane prepolymer is obtained after cooling and serves as a component B.
(4) Weighing 200g of the component A obtained in the step (2), weighing 50g of the component B obtained in the step (3), and mixing A, B to obtain an AB mixture containing MOFs; to the above mixture was added 25.0g of 2-methylimidazole. And (3) stirring uniformly at room temperature, vacuumizing, defoaming, and curing at 60 ℃ for 5 hours to obtain the MOFs-containing epoxy resin/polyurethane IPNs grouting reinforcement material.
Comparative example
Epoxy/polyurethane materials were prepared as comparative examples according to the above process.
(1) Adding 300g of epoxy resin into a three-neck flask with a thermometer, heating to 60 ℃ under the protection of nitrogen, stirring for 30 minutes at constant temperature, and cooling to obtain an epoxy resin prepolymer which is marked as a component A.
(2) 100g of toluene diisocyanate and 100g of polyether polyol (N204) react for 5 hours at the temperature of 60 ℃, and a polyurethane prepolymer is obtained after cooling and serves as a component B.
(3) 200g of component A obtained in (1) and 50g of component B obtained in (2) were weighed, A, B was mixed to prepare an AB mixture, and 25.0g of 2-methylimidazole was added to the above mixture. And (3) stirring uniformly at room temperature, vacuumizing, defoaming, and curing at 60 ℃ for 5 hours to obtain the epoxy resin/polyurethane grouting reinforcement material.
Example 2
(1) 300g of epoxy resin and 0.9g of NH2Adding MIL-125 into a three-neck flask with a thermometer, heating to 60 ℃ under the protection of nitrogen, stirring for 30 minutes at constant temperature, and cooling to obtain a part of ring-opened MOFs functionalized epoxy resin prepolymer which is marked as component A.
(2) 100g of toluene diisocyanate and 100g of polyether polyol (N204) react for 5 hours at the temperature of 60 ℃, and a polyurethane prepolymer is obtained after cooling and serves as a component B.
(3) 200g of the component A obtained in the step (1) and 50g of the component B obtained in the step (2) are weighed, A, B is mixed to prepare an AB mixture containing MOFs, and 25.0g of 2-methylimidazole is added to the mixture. And (3) stirring uniformly at room temperature, vacuumizing, defoaming, and curing at 60 ℃ for 5 hours to obtain the MOFs-containing epoxy resin/polyurethane IPNs grouting reinforcement material.
Example 3
(1) 300g of epoxy resin and 1.8g of NH2Adding MIL-125 into a three-neck flask with a thermometer, heating to 60 ℃ under the protection of nitrogen, stirring for 30 minutes at constant temperature, and cooling to obtain a part of ring-opened MOFs functionalized epoxy resin prepolymer which is marked as component A.
(2) 100g of toluene diisocyanate and 100g of polyether polyol (N204) react for 5 hours at the temperature of 60 ℃, and a polyurethane prepolymer is obtained after cooling and serves as a component B.
(3) 200g of the component A obtained in the step (1) and 50g of the component B obtained in the step (2) are weighed, A, B is mixed to prepare an AB mixture containing MOFs, and 25.0g of 2-methylimidazole is added to the mixture. And (3) stirring uniformly at room temperature, vacuumizing, defoaming, and curing at 60 ℃ for 5 hours to obtain the MOFs-containing epoxy resin/polyurethane IPNs grouting reinforcement material.
Example 4
(1) 300g of epoxy resin and 2.4g of NH2Adding MIL-125 into a three-neck flask with a thermometer, heating to 60 ℃ under the protection of nitrogen gasStirring for 30 minutes at constant temperature, and cooling to obtain a part of ring-opened MOFs functionalized epoxy resin prepolymer which is recorded as a component A.
(2) 100g of toluene diisocyanate and 100g of polyether polyol (N204) are reacted for 5 hours at the temperature of 60 ℃, and a polyurethane prepolymer is obtained after cooling and is used as a component B.
(3) 200g of component A obtained in (1) and 50g of component B obtained in (2) are weighed, A, B is mixed to obtain AB mixture containing MOFs, and 25.0g of 2-methylimidazole is added to the mixture. And (3) stirring uniformly at room temperature, vacuumizing for defoaming, and curing at 60 ℃ for 5 hours to obtain the MOFs-containing epoxy resin/polyurethane IPNs grouting reinforcement material.
Example 5
(1) 300g of epoxy resin and 2.7g of NH2-MIL-125 is added into a three-neck flask with a thermometer, heated to 60 ℃ under the protection of nitrogen, stirred for 30 minutes at constant temperature, and cooled to obtain a part of ring-opened MOFs functionalized epoxy resin prepolymer which is marked as component A.
(2) 100g of toluene diisocyanate and 100g of polyether polyol (N204) are reacted for 5 hours at the temperature of 60 ℃, and a polyurethane prepolymer is obtained after cooling and is used as a component B.
(3) 200g of the component A obtained in the step (1) and 50g of the component B obtained in the step (2) are weighed, A, B is mixed to prepare an AB mixture containing MOFs, and 25.0g of 2-methylimidazole is added to the mixture. And (3) stirring uniformly at room temperature, vacuumizing, defoaming, and curing at 60 ℃ for 5 hours to obtain the MOFs-containing epoxy resin/polyurethane IPNs grouting reinforcement material.
The performance tests of example 1, example 2, example 3, example 4, example 5 and comparative example are carried out, wherein the tensile strength is tested according to the GB/T528 standard; the bonding strength is tested according to the GB/T8808 standard; the oxygen index is tested according to the GB/T2406 standard.
TABLE 1 results of tensile strength, bonding strength, and polar oxygen index testing for MOFs/epoxy resin/polyurethane IPNs grouting materials
The test results show that: as shown in Table 1, it can be seen that the tensile strength and the bonding strength of the epoxy resin/polyurethane modified by the MOFs nano material of the present invention are significantly improved compared to the pure epoxy resin/polyurethane, and the tensile strength and the bonding strength are continuously enhanced with the continuous increase of the MOFs content. When the mass addition amount of the MOFs is 0.3%, the tensile strength is increased from 20.8MPa to 98.6MPa, and the bonding strength is increased from 3.9MPa to 12.3 MPa; meanwhile, according to the flame retardant performance data, when the mass addition amount of the MOFs is 0.3%, the limiting oxygen index of the MOFs/epoxy resin/polyurethane is increased to 23.3, which is attributed to that the introduction of the MOFs porous structure enables more rigid structures in the composite system, so that the chemical stability of the composite system is enhanced.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. A preparation method of MOFs-containing epoxy resin/polyurethane IPNs grouting materials is characterized by comprising the following steps:
step one, weighing MOFs nano material and epoxy resin according to the mass ratio of 0.001: 1-0.01: 1, uniformly mixing, heating to 60-80 ℃ under the protection of nitrogen, stirring at constant temperature for 30-60 minutes, and cooling to obtain a part of ring-opened MOFs functionalized epoxy resin prepolymer serving as a component A;
step two, uniformly mixing isocyanate and polyether polyol according to the mass ratio of 1:1, reacting for 3-5 hours at the temperature of 60-80 ℃, and cooling to obtain a polyurethane prepolymer serving as a component B;
and step three, mixing A, B two components according to the mass ratio of 3: 1-5: 1 to obtain an AB mixture containing MOFs, adding a curing agent into the AB mixture containing MOFs according to the mass ratio of 1: 0.1-1: 0.5, uniformly stirring, vacuumizing and defoaming, and curing in a vacuum drying oven at 40-100 ℃ for 5-10 hours to obtain the epoxy resin/polyurethane IPNs grouting material containing MOFs.
2. The method of claim 1, wherein: in the first step, the MOFs nano material is a coordination type compound which is formed by taking 2-amino terephthalic acid and derivatives thereof as organic chain segments and taking transition metal ions as coordination centers.
3. The method of claim 1, wherein: in the first step, the epoxy resin comprises one of bisphenol a epoxy resin E51, bisphenol a epoxy resin E44 and bisphenol F epoxy resin F51.
4. The method of claim 1, wherein: in the second step, the isocyanate includes one of toluene diisocyanate, 4' -diphenylmethane diisocyanate, and isophorone diisocyanate.
5. The method of claim 1, wherein: in the second step, the polyether polyol comprises one of polyether polyol N204 and polyether polyol N303.
6. The method of claim 1, wherein: in the third step, the curing agent comprises one of 2-methylimidazole, 2-ethylimidazole and 2-ethyl-4-methylimidazole.
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| CN114920495B (en) * | 2022-06-01 | 2023-05-12 | 煤炭科学技术研究院有限公司 | Mining grouting reinforcement filler and preparation method thereof |
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