CN114149681A - Low-temperature silicate modified polyurethane high polymer material and preparation method thereof - Google Patents
Low-temperature silicate modified polyurethane high polymer material and preparation method thereof Download PDFInfo
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- CN114149681A CN114149681A CN202111323479.9A CN202111323479A CN114149681A CN 114149681 A CN114149681 A CN 114149681A CN 202111323479 A CN202111323479 A CN 202111323479A CN 114149681 A CN114149681 A CN 114149681A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
Abstract
The invention discloses a low-temperature silicate modified polyurethane high polymer material and a preparation method thereof, wherein the material comprises a component A and a component B, and the volume ratio of the component A to the component B is 1: 1; the component A comprises the following components in parts by mass: 100 parts of silane coupling agent modified liquid sodium silicate glass and 0-5 parts of catalyst, wherein the component B comprises the following components in parts by weight: 60-65 parts of polyphenyl polymethylene polyisocyanate, 15-20 parts of modified MDI and 0-30 parts of diluent, wherein the modified MDI is prepared by modifying and polymerizing epoxy resin and polyether polyol. The method can effectively reduce the highest reaction temperature of the solidification body while keeping the characteristics of the water glass, and improve the binding power.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a low-temperature silicate modified polyurethane high polymer material and a preparation method thereof.
Background
In the production process of a coal mine, the compressive strength of a coal bed and loose surrounding rocks is low, and potential safety hazards such as roof fall, collapse, underground water seepage and the like are easily generated in a broken and loose surrounding rock area and a fracture development zone under the condition of increasing dynamic pressure. The polymer reinforcing and plugging material is injected into the broken coal rock layer, so that cracks and fissures can be effectively plugged, the broken coal rock bodies are bonded together, the integral supporting force of the coal rock bodies is improved, and the purposes of coal rock reinforcing and plugging are finally achieved.
The commonly used coal-rock body reinforcing agent mainly comprises epoxy resin, urea-formaldehyde resin, polyurethane and the like. The polyurethane reinforcing agent has the advantages of moderate viscosity, adjustable setting time, strong cohesive force, high mechanical strength, high strength after solidification and the like, but has poor flame retardant effect and higher cost.
However, the water glass has better flame retardant property, so that the water glass chemical grouting materials are widely researched, most of the materials have the advantages of good permeability, no toxicity, simple components and the like, but the highest reaction temperature of a bonding body of the water glass materials is usually higher than 100 ℃, and the adhesive force is poor, so that the technical problems to be solved in the field are urgently solved.
Disclosure of Invention
In order to solve the technical problems, the invention provides a low-temperature silicate modified polyurethane high polymer material which has the characteristics of water glass and can effectively reduce the reaction temperature of a solidification body and improve the binding power.
The technical scheme for solving the technical problems is as follows: the low-temperature silicate modified polyurethane high polymer material comprises a component A and a component B, wherein the volume ratio of the component A to the component B is 1: 1;
the component A comprises the following components in parts by mass:
100 parts of silane coupling agent modified liquid sodium silicate water glass,
0 to 5 parts of a catalyst,
the component B comprises the following components in parts by mass:
60 to 65 parts of polyphenyl polymethylene polyisocyanate,
15-20 parts of modified MDI (diphenylmethane diisocyanate),
0 to 30 parts of a diluent, and the like,
the modified MDI is prepared by modifying and polymerizing epoxy resin and polyether polyol.
The low-temperature silicate modified polyurethane high polymer material disclosed by the application has the beneficial effects that: after the component A and the component B are mixed, modified MDI in the component B firstly reacts with water in liquid sodium silicate water glass modified by a silane coupling agent to generate gas-phase carbon dioxide, then the carbon dioxide reacts with sodium silicate aqueous solution to generate orthosilicic acid, the orthosilicic acid reacts with the modified MDI to generate a high molecular polymer to form a tree structure, and Si-0-Si chain segments, polyurethane flexible blocks, expanding chain segments and rigid chain segments contained in the tree structure are mutually staggered, so that the aim of modifying a polyurethane material by the liquid sodium silicate water glass is fulfilled, the highest reaction temperature of a solidified body can be effectively reduced while the characteristics of the water glass are maintained, and the binding power is improved.
In an alternative embodiment, the diluent is dibutyl phthalate.
In an alternative embodiment, the catalyst is an amine catalyst or a catalyst for water glass.
The application also provides a method for preparing the low-temperature silicate modified polyurethane high polymer material, which comprises the following steps:
preparing the component A:
respectively weighing silane coupling agent modified liquid sodium silicate glass and a catalyst according to parts by weight, and uniformly mixing to obtain a component A;
preparing the component B:
respectively weighing the polyphenyl polymethylene polyisocyanate, the modified MDI and the diluent according to the parts by weight, uniformly mixing to obtain a mixture,
heating the mixture to 70-75 ℃ for reaction, and cooling after the reaction is finished to obtain the component B;
and mixing the component A and the component B according to the volume ratio of 1:1 to obtain the low-temperature silicate modified polyurethane high polymer material.
In an alternative embodiment, the silane coupling agent modified liquid sodium silicate waterglass is prepared by the steps of:
under the condition of 20-30 ℃, mixing a silane coupling agent and liquid sodium silicate water glass according to the mass ratio of 1-10: and 90-99, and standing for reaction for more than 2 hours to obtain the silane coupling agent modified liquid sodium silicate water glass.
In an alternative embodiment, in the step of preparing the B component:
and heating the mixture to 70-75 ℃, carrying out heat preservation reaction for more than 2 hours, and then cooling to 20-30 ℃ to obtain the component B.
The application also provides an application of the low-temperature silicate modified polyurethane high polymer material as a coal rock body reinforcing agent.
Detailed Description
The principles and features of the present application are described below in conjunction with embodiments, which are included to explain the present application and are not intended to limit the scope of the present application.
In the following examples disclosed herein, the polyphenyl polymethylene polyisocyanate is available from PM-200, manufactured by Nicotiana Vanhua polyurethane, Inc.; the modified MDI is prepared by modifying and polymerizing epoxy resin and polyether polyol, and more specifically, the modified MDI is produced by MDI-42 produced by Shanxi Lu' an mineral engineering Limited liability company; the diluent is available from Senese chemical Co., Ltd.
For comparison purposes, in the following examples, silane coupling agent modified liquid sodium silicate waterglasses were prepared by the following steps:
and (2) mixing a silane coupling agent and liquid sodium silicate water glass according to the mass ratio of 1:99 at room temperature, and standing for reaction for 2 hours to obtain the silane coupling agent modified liquid sodium silicate water glass.
It is to be understood that in some examples, the silane coupling agent and the liquid sodium silicate waterglass may also be in a mass ratio of 10:90 or 5: 95.
Example 1
The application provides a preparation method of a low-temperature silicate modified polyurethane high polymer material, which specifically comprises the following steps:
step S1: taking sufficient silane coupling agent modified liquid sodium silicate water glass as a component A;
step S201: weighing 62kg of polyphenyl polymethylene polyisocyanate, 15.6kg of modified MDI and 22.4kg of dibutyl phthalate, and fully stirring and mixing the components in a reaction kettle at room temperature;
step S202: heating the reaction kettle to 70 ℃ and keeping the temperature for 2 hours, then cooling the reaction kettle to room temperature, and filling nitrogen into the cooled product for replacement and packaging to obtain a component B;
step S3: and mixing and grouting the component A and the component B according to the volume ratio of 1:1 by adopting a double-liquid grouting pump to obtain the low-temperature silicate modified polyurethane high polymer material disclosed by the application.
Example 2
The application provides a preparation method of a low-temperature silicate modified polyurethane high polymer material, which specifically comprises the following steps:
step S1: weighing 100kg of silane coupling agent modified liquid sodium silicate glass and 5kg of amine catalyst, and mixing to obtain a component A;
step S201: weighing 61.4kg of polyphenyl polymethylene polyisocyanate, 15.6kg of modified MDI and 23kg of dibutyl phthalate, and fully stirring and mixing the components in a reaction kettle at room temperature;
step S202: heating the reaction kettle to 70 ℃ and keeping the temperature for 2 hours, then cooling the reaction kettle to room temperature, and filling nitrogen into the cooled product for replacement and packaging to obtain a component B;
step S3: and mixing and grouting the component A and the component B according to the volume ratio of 1:1 by adopting a double-liquid grouting pump to obtain the low-temperature silicate modified polyurethane high polymer material disclosed by the application.
Example 3
The application provides a preparation method of a low-temperature silicate modified polyurethane high polymer material, which specifically comprises the following steps:
step S1: 100kg of silane coupling agent modified liquid sodium silicate glass and 1kg of a special catalyst for water glass (purchased from Guangzhou Youyun synthetic materials Co., Ltd., type: CUCAT-WNT) are weighed and mixed to obtain a component A;
step S201: weighing 60kg of polyphenyl polymethylene polyisocyanate, 15kg of modified MDI and 25kg of dibutyl phthalate, and fully stirring and mixing the components in a reaction kettle at room temperature;
step S202: heating the reaction kettle to 70 ℃ and keeping the temperature for 2 hours, then cooling the reaction kettle to room temperature, and filling nitrogen into the cooled product for replacement and packaging to obtain a component B;
step S3: and mixing and grouting the component A and the component B according to the volume ratio of 1:1 by adopting a double-liquid grouting pump to obtain the low-temperature silicate modified polyurethane high polymer material disclosed by the application.
Example 4
The performance of the low-temperature silicate-modified polyurethane polymer materials prepared in the above examples 1 to 3 was tested according to AQ/T1089-
TABLE 1
| Item | Highest reaction temperature of solidified body/. degree.C | Expansion multiple speed | Compressive strength/Mpa | Adhesive strength/Mpa | Oxygen index/% |
| Example 1 | 99.2 | 1.0 | 41 | 5 | 29 |
| Example 2 | 99.1 | 1.0 | 41 | 5 | 29 |
| Example 3 | 98 | 1.0 | 40 | 5 | 30 |
The data in table 1 show that the highest reaction temperature of the consolidated body of the low-temperature silicate-modified polyurethane polymer material prepared in each embodiment of the application is lower than 100 ℃, and the low-temperature silicate-modified polyurethane polymer material has better compressive strength and bonding strength, and simultaneously maintains the flame retardant property of water glass materials, so that the low-temperature silicate-modified polyurethane polymer material has good application prospect in coal and rock stratum reinforcement, and is particularly suitable for rapid reinforcement and plugging treatment of broken coal beds and rock stratums in various poorly ventilated coal mines, tunnels and tunnels.
In the description of the present specification, "a plurality" means at least two, e.g., two, three, etc., unless explicitly defined otherwise.
In the description herein, reference to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the application. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
The terms used in the present specification are those general terms currently widely used in the art in consideration of functions related to the present disclosure, but they may be changed according to the intention of a person having ordinary skill in the art, precedent, or new technology in the art. Also, specific terms may be selected by the applicant, and in this case, their detailed meanings will be described in the detailed description of the present disclosure. Therefore, the terms used in the specification should not be construed as simple names but based on the meanings of the terms and the overall description of the present disclosure.
The description uses words to describe operational steps performed in accordance with embodiments of the present application. It should be understood that the operational steps in the embodiments of the present application are not necessarily performed in the exact order recited. Rather, the various steps may be processed in reverse order or simultaneously, as desired. Meanwhile, other operations may be added to the processes, or a certain step or several steps of operations may be removed from the processes.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (7)
1. The low-temperature silicate modified polyurethane high polymer material is characterized by comprising a component A and a component B, wherein the volume ratio of the component A to the component B is 1: 1;
the component A comprises the following components in parts by mass:
100 parts of silane coupling agent modified liquid sodium silicate water glass,
0 to 5 parts of a catalyst,
the component B comprises the following components in parts by mass:
60 to 65 parts of polyphenyl polymethylene polyisocyanate,
15-20 parts of modified MDI (diphenylmethane diisocyanate),
0 to 30 parts of a diluent, and the like,
the modified MDI is prepared by modifying and polymerizing epoxy resin and polyether polyol.
2. The low-temperature silicate-modified polyurethane polymer material according to claim 1, wherein the diluent is dibutyl phthalate.
3. The low-temperature silicate-modified polyurethane polymer material according to claim 1, wherein the catalyst is an amine catalyst or a catalyst for water glass.
4. A method for preparing the low-temperature silicate-modified polyurethane polymer material as claimed in any one of claims 1 to 3, which comprises the following steps:
preparing the component A:
respectively weighing silane coupling agent modified liquid sodium silicate glass and a catalyst according to parts by weight, and uniformly mixing to obtain a component A;
preparing the component B:
respectively weighing the polyphenyl polymethylene polyisocyanate, the modified MDI and the diluent according to the parts by weight, uniformly mixing to obtain a mixture,
heating the mixture to 70-75 ℃ for reaction, and cooling after the reaction is finished to obtain the component B;
and mixing the component A and the component B according to the volume ratio of 1:1 to obtain the low-temperature silicate modified polyurethane high polymer material.
5. The method of claim 4, wherein the silane coupling agent modified liquid sodium silicate waterglass is prepared by:
mixing a silane coupling agent and liquid sodium silicate water glass according to the mass ratio of 1-10: 90-99 at the temperature of 20-30 ℃, and standing for reaction for more than 2 hours to obtain the silane coupling agent modified liquid sodium silicate water glass.
6. The method of claim 4, wherein in the step of preparing the B-side component:
and heating the mixture to 70-75 ℃, carrying out heat preservation reaction for more than 2 hours, and then cooling to 20-30 ℃ to obtain the component B.
7. Use of the low-temperature silicate-modified polyurethane polymer material as defined in any one of claims 1 to 3 as a coal-rock mass reinforcing agent.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1391440A1 (en) * | 2002-08-22 | 2004-02-25 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Chemical grout composition for stabilization when digging tunnels and construction method for increasing stability using same |
| CN111234172A (en) * | 2020-01-17 | 2020-06-05 | 阳泉煤业（集团）有限责任公司 | Epoxy resin/water glass/polyurethane composite reinforced material and preparation method thereof |
| CN112225523A (en) * | 2020-10-20 | 2021-01-15 | 陕西煤业化工技术研究院有限责任公司 | Silicate modified polyurethane reinforcing material and preparation method and application thereof |
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- 2021-11-08 CN CN202111323479.9A patent/CN114149681A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1391440A1 (en) * | 2002-08-22 | 2004-02-25 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Chemical grout composition for stabilization when digging tunnels and construction method for increasing stability using same |
| CN111234172A (en) * | 2020-01-17 | 2020-06-05 | 阳泉煤业（集团）有限责任公司 | Epoxy resin/water glass/polyurethane composite reinforced material and preparation method thereof |
| CN112225523A (en) * | 2020-10-20 | 2021-01-15 | 陕西煤业化工技术研究院有限责任公司 | Silicate modified polyurethane reinforcing material and preparation method and application thereof |
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