CN116854955B - Hydroxymethylurea-PTGE-carboxymethyl cellulose antifreeze and water-resistant sand-fixing material and preparation method thereof - Google Patents
Hydroxymethylurea-PTGE-carboxymethyl cellulose antifreeze and water-resistant sand-fixing material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a methylol urea-PTGE-carboxymethyl cellulose antifreezing water-resistant sand-fixing material and a preparation method thereof. The preparation method comprises the following steps: and (3) carrying out free radical polymerization reaction on a mixed reaction system containing carboxymethyl cellulose salt, hydroxymethyl urea and PTGE under the action of an initiator to obtain the hydroxymethyl urea-PTGE-carboxymethyl cellulose antifreezing water-resistant sand-fixing material. The invention utilizes the methylol urea to improve the consolidation strength, and uses the glycerol triglycidyl ether to improve the cold resistance and the water resistance, so as to prepare the methylol urea-PTGE-carboxymethyl cellulose (HDM-PTGE-CMC) sand-fixing material suitable for the wet low-temperature Qinghai-Tibet plateau alpine sandy land after rain, and the sand-fixing material has the advantages of low temperature resistance, strong bonding strength and water resistance.
Description
Technical Field
The invention relates to a sand-fixing agent, in particular to a hydroxymethyl urea-PTGE-carboxymethyl cellulose (HDM-PTGE-CMC) antifreezing water-resistant sand-fixing material, a preparation method and application thereof, and belongs to the technical field of biological polymers and sand fixation.
Background
Desertification seriously threatens the sustainable development of global ecological safety and human economy society, affects 25% of global land total area, threatens the life of more than 10 hundred million population of more than 100 countries, and is a serious environmental problem and development bottleneck facing the world. Windblown sand activity is a typical surface process in desert areas. Therefore, the necessary measures are significant in wind prevention and sand fixation and sand resistance.
The average annual temperature of the daily dry arbor ecological protection area at the southeast edge of the Qinghai-Tibet plateau is about 2.55 ℃, the minimum annual temperature is about-23 ℃, the annual precipitation is about 801.76mm, which is more than 440.86mm compared with the annual precipitation of the Qinghai-Hu eastern ecological protection area at the northbound of the Qinghai-Tibet plateau, such as Gao Yuandong, so that the environment temperature after the high-cold sand land in the Qinghai-Tibet plateau is rainy is low, the humidity is high, and the sand-fixing agent suitable for the area needs to have better anti-freezing water resistance.
The long chain structure of the carboxymethyl cellulose (CMC) ensures that the CMC has good cohesiveness and film forming property, but is extremely easy to decompose, has low consolidation strength, and has high freezing resistance and water resistance. Acrylamide is commonly used for enhancing the action between cellulose and derivatives thereof in the prior art, but the acrylamide has toxicity and risks uncertainty on human health and ecological environment. Therefore, it is significant to find a novel nontoxic substance to replace acrylamide to enhance carboxymethyl cellulose.
Disclosure of Invention
The invention aims to improve the consolidation strength of the carboxymethyl urea and improve the cold resistance and the water resistance of the carboxymethyl urea by using glycerol triglycidyl ether, and provides a hydroxymethyl urea-PTGE-carboxymethyl cellulose (HDM-PTGE-CMC) sand-fixing material suitable for wet low-temperature Qinghai-Tibet plateau high-cold sand areas after rain and a preparation method thereof, so as to overcome the defects of easy decomposition, low consolidation strength and low thermal stability of carboxymethyl fibers in the prior art.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method of a methylol urea-PTGE-carboxymethyl cellulose antifreezing water-resistant sand-fixing material, which comprises the following steps: and (3) carrying out free radical polymerization reaction on a mixed reaction system containing carboxymethyl cellulose salt, hydroxymethyl urea and PTGE under the action of an initiator to obtain the hydroxymethyl urea-PTGE-carboxymethyl cellulose antifreezing water-resistant sand-fixing material.
In some embodiments, the method of making comprises: and (3) introducing protective gas into the mixed reaction system at the temperature of between 65 and 100 ℃, adding an initiator, and fully reacting for 3 to 6 hours to obtain the hydroxymethyl urea-PTGE-carboxymethyl cellulose antifreezing water-resistant sand-fixing material.
The embodiment of the invention also provides the methylol urea-PTGE-carboxymethyl cellulose antifreezing water-resistant sand-fixing material prepared by the preparation method.
Further, the embodiment of the invention also provides the application of the hydroxymethyl urea-PTGE-carboxymethyl cellulose antifreezing water-resistant sand-fixing material in the sand-fixing field.
Compared with the prior art, the invention has the beneficial effects that:
The invention utilizes the methylol urea to improve the consolidation strength, and uses the glycerol triglycidyl ether to improve the cold resistance and the water resistance, so as to prepare the methylol urea-PTGE-carboxymethyl cellulose (HDM-PTGE-CMC) sand-fixing material suitable for the wet low-temperature Qinghai-Tibet plateau alpine sandy land after rain, and the sand-fixing material has the advantages of low temperature resistance, strong bonding strength and water resistance.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present invention, and other drawings may be obtained according to the drawings without inventive effort to those skilled in the art.
FIG. 1 is a schematic representation of the preparation of an exemplary embodiment of the freeze-resistant, water-tolerant, sand-stabilizing material of methylol urea-PTGE-carboxymethyl cellulose (HDM-PTGE-CMC) of the present invention.
Detailed Description
Aiming at the defects of the prior art, the inventor provides a technical scheme of the invention through long-term research and a large amount of practice, mainly utilizes hydroxymethyl urea to strengthen the mechanical strength of carboxymethyl cellulose, uses PTGE to strengthen the anti-freezing performance and the water resistance of an HDM-CMC sand fixing agent, and prepares the anti-freezing water-resistant hydroxymethyl urea-PTGE-carboxymethyl cellulose (HDM-PTGE-CMC) sand fixing material which can be used for wet Qinghai-Tibet plateau alpine sandy land after rain. The technical scheme, the implementation process, the principle and the like are further explained as follows. It should be understood that within the scope of the present invention, the above-described features of the present invention and features specifically described in the following (embodiments) may be combined with each other to constitute new or preferred embodiments. And are limited to a space, and are not described in detail herein.
As another aspect of the technical scheme of the invention, the preparation method of the hydroxymethyl urea-glycerol triglycidyl ether-carboxymethyl cellulose (HDM-PTGE-CMC) antifreezing water-resistant sand-fixing material comprises the following steps: and (3) carrying out free radical polymerization reaction on a mixed reaction system containing carboxymethyl cellulose salt, hydroxymethyl urea and PTGE under the action of an initiator to obtain the hydroxymethyl urea-PTGE-carboxymethyl cellulose antifreezing water-resistant sand-fixing material.
In some embodiments, the method of making comprises: and mixing carboxymethyl cellulose salt with water to form carboxymethyl cellulose salt water solution, regulating the pH value of the carboxymethyl cellulose salt water solution to be 6-9 by using alkaline substances, and then adding methylol urea and PTGE to form the mixed reaction system.
Further, the initial pH values may be 6, 7, 8, 9, etc., respectively, but are not limited thereto.
Further, in the mixed reaction system, the molar ratio of the carboxymethyl cellulose salt to the methylol urea to PTGE is 1:1:1-1:2:2.
The methylol urea (Hydroxymethyl urea, HDM) adopted by the invention is a nitrogen-containing organic matter, has a molecular formula of C 2H6N2O2, contains amide, amino, hydroxyl and carboxyl groups, and is mainly generated by taking non-protein nitrogen (NPN) as a main raw material. NPN refers to a non-protein nitrogen-containing compound, which comprises amino acid, skin, ammonia and derivatives thereof, urea and derivatives thereof, amines, halamine, hey, throat, nitrate, alkaloid and the like, and widely exists in organisms of animals and plants, is a nontoxic and naturally degradable material, and amino groups and hydroxyl groups and amide groups of the NPN can replace hydrogen bonding between acrylamide and cellulose and derivatives thereof to form a stable crosslinked network, so that the mechanical properties of the cellulose and derivatives thereof are enhanced.
Further, the carboxymethyl cellulose salt includes any one or a combination of two or more of sodium carboxymethyl cellulose, lithium carboxymethyl cellulose, potassium carboxymethyl cellulose, calcium carboxymethyl cellulose, ammonium carboxymethyl cellulose, etc., but is not limited thereto.
Glycerol triglycidyl ether (PTGE) not only has good water resistance, but also is commonly used to improve the low temperature toughness of rigid structures due to the large number of ether linkages. The flexible chain segment PTGE is introduced into the crosslinked network, so that the flexibility of the network chain molecule can be improved, the internal stress is reduced, and the balance of low-temperature toughness and bonding strength is obtained by regulating the crosslinking density. And the epoxy groups in the glycerol triglycidyl ether (PTGE) can be tightly combined with the flexible long chain through the hydrophilic groups to form a dense crosslinked network, so that the low temperature resistance, the strong bonding strength and the water resistance of the carboxymethyl cellulose are enhanced.
In some embodiments, the preparation method may specifically include: introducing protective gas into the mixed reaction system at 65-100 ℃, adding an initiator, and fully reacting for 3-6 hours to obtain the hydroxymethyl urea-glycerol triglycidyl ether-carboxymethyl cellulose (HDM-PTGE-CMC) antifreezing water-resistant sand-fixing material.
Further, the reaction temperature may be 65 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃ and the like, respectively, but is not limited thereto.
Further, the reaction time may be 3h, 4h, 5h, 6h, etc., respectively, but is not limited thereto.
The sand fixing material with the anti-freezing water resistance has the following action mechanism: when the HDM-PTGE-CMC sand fixing agent is sprayed in a sand table, carbonyl groups on a methylol urea chain can carry out complexation reaction with inorganic ions in sand, and substances such as calcium carbonate in gravel can carry out displacement reaction with carboxymethyl cellulose to replace sodium ions, so that two carboxyl anions and one inorganic cation (such as calcium ions and magnesium ions) are combined to become a stable reticular structure, and the sand fixing effect is achieved. And the epoxy group in the glycerol triglycidyl ether (PTGE) can be tightly combined with the flexible long chain through the hydrophilic group, and the epoxy group can be subjected to ring opening reaction with the phenolic hydroxyl group on the benzene ring under alkaline conditions to form an ether bond, so that a dense crosslinked network is formed, and the low temperature resistance, the strong adhesive strength and the water resistance of the carboxymethyl cellulose are enhanced.
Further, the initiator may be potassium persulfate (K 2S2O8), but is not limited thereto.
Further, the initiator may be added to the mixed reaction system at a concentration of 0.05 to 0.25g/mL, for example, 0.05g/mL, 0.1g/mL, 0.15g/mL, 0.2g/mL, 0.25g/mL, etc., but is not limited thereto.
Further, the inert gas may be nitrogen, but is not limited thereto.
Another aspect of the embodiments of the present invention also provides a methylol urea-glycerol triglycidyl ether-carboxymethyl cellulose (HDM-PTGE-CMC) antifreeze water-tolerant sand-fixing material prepared by the foregoing preparation method.
Further, the water permeability coefficient of the methylol urea-PTGE-carboxymethyl cellulose antifreezing water-resistant sand-fixing material is 5x10 -4cm/s～1.5x10-3 cm/s, and the compression strength of the sand-fixing sample is 4-6 MPa. After curing for 8 hours, the bonding strength at the liquid nitrogen temperature (-210 to minus 196 ℃) is between 3 and 7 MPa.
Accordingly, another aspect of the embodiments of the present invention also provides the use of any of the methylol urea-PTGE-carboxymethyl cellulose freeze-resistant, water-tolerant, sand-fixing materials described above in the field of sand fixation, such as in the preparation of sand-fixing materials, or in sand-fixing devices.
By means of the technical scheme, the solidifying strength of the sand-fixing material is improved by utilizing the hydroxymethyl urea, the cold resistance and the water resistance of the sand-fixing material are improved by utilizing the glycerol triglycidyl ether, and the hydroxymethyl urea-PTGE-carboxymethyl cellulose (HDM-PTGE-CMC) sand-fixing material which is suitable for wet low-temperature Qinghai-Tibet plateau alpine sandy regions after rain is prepared, so that the sand-fixing material has the advantages of low temperature resistance, strong bonding strength and water resistance, and can be used in the sand-fixing field.
In order to make the objects, technical solutions and applications of the present invention more clear, the technical solutions of the present invention will be further described in detail below with reference to several preferred embodiments and attached drawings, wherein the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The implementation conditions used in the following examples may be further adjusted according to actual needs, and the implementation conditions not specified are generally those in routine experiments.
Example 1
Deionized water was added to 10g of sodium carboxymethylcellulose (CMC) and stirred sufficiently to obtain an aqueous CMC solution, the aqueous CMC solution was adjusted to pH 8 with NaOH (analytically pure), and monomeric methylol urea (HDM, analytically pure) was added to PTGE to give a molar ratio of carboxymethylcellulose salt, methylol urea, PTGE of 1:1:1.
Then, nitrogen was introduced and stirred for 30 minutes, and after complete dissolution, an initiator potassium persulfate solution (K 2S2O8, analytical grade) was slowly added dropwise at a concentration of 0.05g/mL. After the dripping is finished, the reaction system is placed into a constant-temperature water bath kettle with the temperature of 90 ℃, and is stirred for 4 hours by a stirrer with the speed of 500r/min, so that CMC and HDM are subjected to free radical polymerization under the action of an initiator potassium persulfate, and the reaction process is shown in figure 1. After reacting for 4 hours at the constant temperature of 90 ℃, precipitating the product by ethanol (CH 3CH2 OH, analytically pure), centrifuging by a centrifuge (with the rotating speed of 3500 r/min), fully washing the product by ethanol, purifying by acetone (CH 3COCH3, analytically pure), and drying at 65 ℃ to obtain the HDM-PTGE-CMC sand fixation sample.
Example 2
Deionized water was added to 10g of sodium carboxymethylcellulose (CMC) and stirred sufficiently to obtain an aqueous CMC solution, the aqueous CMC solution was adjusted to pH 8 with NaOH (analytically pure), and monomeric methylol urea (HDM, analytically pure) was added to PTGE to give a molar ratio of carboxymethylcellulose salt, methylol urea, PTGE of 1:2:1.
Then, nitrogen was introduced and stirred for 30 minutes, and after complete dissolution, 0.05g of an initiator potassium persulfate solution (K 2S2O8, analytical grade) was slowly added dropwise at a concentration of 0.1g/mL. After the dripping is finished, the reaction system is placed into a constant-temperature water bath kettle with the temperature of 90 ℃, and is stirred for 4 hours by a stirrer with the speed of 500r/min, so that CMC and HDM are subjected to free radical polymerization under the action of an initiator potassium persulfate, and the reaction process is shown in figure 1. After reacting for 4 hours at the constant temperature of 90 ℃, precipitating the product by ethanol (CH 3CH2 OH, analytically pure), centrifuging by a centrifuge (with the rotating speed of 3500 r/min), fully washing the product by ethanol, purifying by acetone (CH 3COCH3, analytically pure), and drying at 65 ℃ to obtain the HDM-PTGE-CMC sand fixation sample.
Example 3
Deionized water was added to 10g of sodium carboxymethylcellulose (CMC) and stirred sufficiently to obtain an aqueous CMC solution, the aqueous CMC solution was adjusted to pH 8 with NaOH (analytically pure), and monomeric methylol urea (HDM, analytically pure) was added to PTGE to give a molar ratio of carboxymethylcellulose salt, methylol urea, PTGE of 1:2:2.
Then, nitrogen was introduced and stirred for 30 minutes, and after complete dissolution, an initiator potassium persulfate solution (K 2S2O8, analytical grade) was slowly added dropwise at a concentration of 0.10g/mL. After the dripping is finished, the reaction system is placed into a constant-temperature water bath kettle with the temperature of 90 ℃, and is stirred for 4 hours by a stirrer with the speed of 500r/min, so that CMC and HDM are subjected to free radical polymerization under the action of an initiator potassium persulfate, and the reaction process is shown in figure 1. After reacting for 4 hours at the constant temperature of 90 ℃, precipitating the product by ethanol (CH 3CH2 OH, analytically pure), centrifuging by a centrifuge (with the rotating speed of 3500 r/min), fully washing the product by ethanol, purifying by acetone (CH 3COCH3, analytically pure), and drying at 65 ℃ to obtain the HDM-PTGE-CMC sand fixation sample.
The inventor also tests the anti-freezing performance, mechanical strength, water resistance and the like of the sand fixing material obtained in the embodiment, and the results are as follows:
In example 1, the resulting HDM-PTGE-CMC had a water permeability coefficient of 1X10 -3 cm/s and a sand fixation sample compressive strength of 4MPa. After curing for 8 hours, the bonding strength at the liquid nitrogen temperature (-210-196 ℃ C.) was 4MPa.
In example 2, the resulting HDM-PTGE-CMC had a water permeability coefficient of 0.5X10- -3 cm/s and a sand fixation test specimen compressive strength of 5MPa. After curing for 8 hours, the bonding strength at the liquid nitrogen temperature (-210-196 ℃ C.) was 6MPa.
In example 3, the resulting HDM-PTGE-CMC had a water permeability coefficient of 5x10 -4 cm/s and a sand fixation sample compressive strength of 6MPa. After curing for 8 hours, the bonding strength at the liquid nitrogen temperature (-210-196 ℃ C.) was 7MPa.
Example 4
Deionized water was added to 10g of sodium carboxymethylcellulose (CMC) and stirred sufficiently to obtain an aqueous CMC solution, the aqueous CMC solution was adjusted to pH 8 with NaOH (analytically pure), and monomeric methylol urea (HDM, analytically pure) was added to PTGE to give a molar ratio of carboxymethylcellulose salt, methylol urea, PTGE of 1:2:2.
Then, nitrogen was introduced and stirred for 30 minutes, and after complete dissolution, an initiator potassium persulfate solution (K 2S2O8, analytical grade) was slowly added dropwise at a concentration of 0.15g/mL. After the dripping is finished, the reaction system is placed into a constant-temperature water bath kettle with the temperature of 90 ℃, and is stirred for 4 hours by a stirrer with the speed of 500r/min, so that CMC and HDM are subjected to free radical polymerization under the action of an initiator potassium persulfate, and the reaction process is shown in figure 1. After reacting for 4 hours at the constant temperature of 90 ℃, precipitating the product by ethanol (CH 3CH2 OH, analytically pure), centrifuging by a centrifuge (with the rotating speed of 3500 r/min), fully washing the product by ethanol, purifying by acetone (CH 3COCH3, analytically pure), and drying at 65 ℃ to obtain the HDM-PTGE-CMC sand fixation sample.
Example 5
Deionized water was added to 10g of sodium carboxymethylcellulose (CMC) and stirred sufficiently to obtain an aqueous CMC solution, the aqueous CMC solution was adjusted to pH 8 with NaOH (analytically pure), and monomeric methylol urea (HDM, analytically pure) was added to PTGE to give a molar ratio of carboxymethylcellulose salt, methylol urea, PTGE of 1:2:2.
Then, nitrogen was introduced and stirred for 30 minutes, and after complete dissolution, an initiator potassium persulfate solution (K 2S2O8, analytical grade) was slowly added dropwise at a concentration of 0.15g/mL. After the dripping is finished, the reaction system is placed into a constant-temperature water bath kettle with the temperature of 90 ℃, and is stirred for 5 hours by a stirrer with the speed of 500r/min, so that CMC and HDM are subjected to free radical polymerization under the action of an initiator potassium persulfate, and the reaction process is shown in figure 1. After reacting for 5 hours at the constant temperature of 90 ℃, precipitating the product by ethanol (CH 3CH2 OH, analytically pure), centrifuging by a centrifuge (with the rotating speed of 3500 r/min), fully washing the product by ethanol, purifying by acetone (CH 3COCH3, analytically pure), and drying at the temperature of 65 ℃ to obtain the HDM-PTGE-CMC sand fixation sample.
Example 6
Deionized water was added to 10g of ammonium carboxymethyl cellulose, and the mixture was stirred sufficiently to obtain an aqueous CMC solution, which was adjusted to a pH of 9 with an aqueous NaOH solution (analytically pure), and monomeric methylol urea (HDM, analytically pure) PTGE was added to give a molar ratio of carboxymethyl cellulose salt, methylol urea, PTGE of 1:2:2.
Then, nitrogen was introduced and stirred for 30 minutes, and after complete dissolution, an initiator potassium persulfate solution (K 2S2O8, analytical grade) was slowly added dropwise at a concentration of 0.15g/mL. After the dripping is finished, the reaction system is placed into a constant-temperature water bath kettle with the temperature of 80 ℃, and is stirred for 4 hours by a stirrer with the speed of 500r/min, so that CMC and HDM are subjected to free radical polymerization under the action of an initiator potassium persulfate, and the reaction process is shown in figure 1. After reacting for 4 hours at the constant temperature of 80 ℃, precipitating the product by ethanol (CH 3CH2 OH, analytically pure), centrifuging by a centrifuge (with the rotating speed of 3500 r/min), fully washing the product by ethanol, purifying by acetone (CH 3COCH3, analytically pure), and drying at 65 ℃ to obtain the HDM-PTGE-CMC sand fixation sample.
The inventor also tests the anti-freezing performance, mechanical strength, water resistance and the like of the sand fixing material obtained in the embodiment, and the results are as follows:
in example 4, the resulting HDM-PTGE-CMC had a water permeability coefficient of 1X10 -3 cm/s and a sand fixation test specimen compressive strength of 4.5MPa. After curing for 8 hours, the bonding strength at the liquid nitrogen temperature (-210-196 ℃ C.) was 5MPa.
In example 5, the resulting HDM-PTGE-CMC had a water permeability coefficient of 0.5X10- -3 cm/s and a sand fixation test specimen compressive strength of 5.5MPa. After curing for 8 hours, the bonding strength at the liquid nitrogen temperature (-210-196 ℃ C.) was 6MPa.
In example 6, the resulting HDM-PTGE-CMC had a water permeability coefficient of 5.5X10- -4 cm/s and a sand fixation sample compressive strength of 6MPa. After curing for 8 hours, the bonding strength at the liquid nitrogen temperature (-210-196 ℃ C.) was 7MPa.
Example 7
Deionized water was added to 10g of carboxymethylcellulose calcium and stirred sufficiently to obtain a CMC aqueous solution, the pH was adjusted to 6 with an aqueous NaOH solution (analytically pure), and monomeric methylol urea (HDM, analytically pure) PTGE was added to give a molar ratio of carboxymethylcellulose salt, methylol urea, PTGE of 1:2:2.
Then, nitrogen was introduced and stirred for 30 minutes, and after complete dissolution, an initiator potassium persulfate solution (K 2S2O8, analytical grade) was slowly added dropwise at a concentration of 0.25g/mL. After the dripping is finished, the reaction system is placed into a water bath kettle with constant temperature of 70 ℃, and is stirred for 6 hours by a stirrer with speed of 500r/min, so that CMC and HDM are subjected to free radical polymerization under the action of an initiator potassium persulfate, and the reaction process is shown in figure 1. After reacting for 6 hours at the constant temperature of 70 ℃, precipitating the product by ethanol (CH 3CH2 OH, analytically pure), centrifuging by a centrifuge (with the rotating speed of 3500 r/min), fully washing the product by ethanol, purifying by acetone (CH 3COCH3, analytically pure), and drying at the temperature of 65 ℃ to obtain the HDM-PTGE-CMC sand fixation sample.
Example 8
Deionized water was added to 10g of potassium carboxymethyl cellulose, and the mixture was stirred sufficiently to obtain an aqueous CMC solution, which was adjusted to pH 7 with an aqueous NaOH solution (analytically pure), and monomeric methylol urea (HDM, analytically pure) PTGE was added to give a molar ratio of carboxymethyl cellulose salt, methylol urea, PTGE of 1:2:2.
Then, nitrogen was introduced and stirred for 30 minutes, and after complete dissolution, an initiator potassium persulfate solution (K 2S2O8, analytical grade) was slowly added dropwise at a concentration of 0.25g/mL. After the dripping is finished, the reaction system is placed into a water bath kettle with constant temperature of 100 ℃, and is stirred for 3 hours by a stirrer with speed of 500r/min, so that CMC and HDM are subjected to free radical polymerization under the action of an initiator potassium persulfate, and the reaction process is shown in figure 1. After reacting for 3 hours at the constant temperature of 100 ℃, precipitating the product by ethanol (CH 3CH2 OH, analytically pure), centrifuging by a centrifuge (with the rotating speed of 3500 r/min), fully washing the product by ethanol, purifying by acetone (CH 3COCH3, analytically pure), and drying at 65 ℃ to obtain the HDM-PTGE-CMC sand fixation sample.
Example 9
Deionized water was added to 10g of lithium carboxymethyl cellulose and stirred sufficiently to obtain an aqueous CMC solution, the pH was adjusted to 8 with an aqueous NaOH solution (analytically pure), and monomeric methylol urea (HDM, analytically pure) PTGE was added to give a molar ratio of carboxymethyl cellulose salt, methylol urea, PTGE of 1:2:2.
Then, nitrogen was introduced and stirred for 30 minutes, and after complete dissolution, an initiator potassium persulfate solution (K 2S2O8, analytical grade) was slowly added dropwise at a concentration of 0.20g/mL. After the dripping is finished, the reaction system is placed into a constant-temperature water bath kettle with the temperature of 65 ℃, and is stirred for 6 hours by a stirrer with the speed of 500r/min, so that CMC and HDM are subjected to free radical polymerization under the action of an initiator potassium persulfate, and the reaction process is shown in figure 1. After reacting for 6 hours at the constant temperature of 65 ℃, precipitating the product by ethanol (CH 3CH2 OH, analytically pure), centrifuging by a centrifuge (with the rotating speed of 3500 r/min), fully washing the product by ethanol, purifying by acetone (CH 3COCH3, analytically pure), and drying at the temperature of 65 ℃ to obtain an HDM-PTGE-CMC sand fixation sample.
The inventor also tests the anti-freezing performance, mechanical strength, water resistance and the like of the sand fixing material obtained in the embodiment, and the results are as follows:
In example 7, the resulting HDM-PTGE-CMC had a water permeability coefficient of 1.5X10- -3 cm/s and a sand fixation test specimen compressive strength of 6MPa. After curing for 8 hours, the bonding strength at the liquid nitrogen temperature (-210-196 ℃ C.) was 5MPa.
In example 8, the resulting HDM-PTGE-CMC had a water permeability coefficient of 7X10 -4 cm/s cm/s and a sand fixation specimen compression strength of 5.6MPa. After curing for 8 hours, the bonding strength at the liquid nitrogen temperature (-210-196 ℃ C.) was 7MPa.
In example 9, the resulting HDM-PTGE-CMC had a water permeability coefficient of 0.5X10 -3 cm/s and a sand fixation test specimen compressive strength of 6.0MPa. After curing for 8 hours, the bonding strength at the liquid nitrogen temperature (-210-196 ℃ C.) was 6MPa.
Comparative example 1
This comparative example differs from example 1 in that: no methylol urea was added. The water permeability coefficient of the obtained sand-fixing material is 2x10 -3 cm/s, and the compressive strength of the sand-fixing sample is 4MPa. After curing for 8 hours, the bonding strength at the liquid nitrogen temperature (-210-196 ℃ C.) was 4MPa.
Comparative example 2
This comparative example differs from example 1 in that: PTGE was not added. The water permeability coefficient of the obtained sand-fixing material is 1.5x10 -3 cm/s, and the compressive strength of the sand-fixing sample is 5MPa. After curing for 8 hours, the bonding strength at the liquid nitrogen temperature (-210-196 ℃ C.) was 3MPa.
In addition, the inventors have conducted experiments with other materials, process operations, and process conditions as described in this specification with reference to the foregoing examples, and have all obtained desirable results.
It should be understood that the above examples are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and implement the same according to the present invention without limiting the scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.
Claims (7)
1. The preparation method of the methylol urea-PTGE-carboxymethyl cellulose antifreezing water-resistant sand-fixing material is characterized by comprising the following steps:
Mixing carboxymethyl cellulose salt with water to form carboxymethyl cellulose salt water solution, regulating the pH value of the carboxymethyl cellulose salt water solution to be 6-9 by an alkaline substance, and then adding methylol urea and glycerol triglycidyl ether (PTGE) to form the mixed reaction system; the molar ratio of the carboxymethyl cellulose salt to the methylol urea to the glycerol triglycidyl ether in the mixed reaction system is 1:1: 1-1: 2:2;
and (3) introducing protective gas into the mixed reaction system at the temperature of 65-100 ℃, adding an initiator, and fully performing free radical polymerization for 3-6 hours to obtain the hydroxymethyl urea-PTGE-carboxymethyl cellulose antifreezing water-resistant sand-fixing material.
2. The method of manufacturing according to claim 1, characterized in that: the carboxymethyl cellulose salt comprises any one or more than two of sodium carboxymethyl cellulose, lithium carboxymethyl cellulose, potassium carboxymethyl cellulose, calcium carboxymethyl cellulose and ammonium carboxymethyl cellulose.
3. The method of manufacturing according to claim 1, characterized in that: and the concentration of the initiator added into the mixed reaction system is 0.05-0.25 g/mL.
4. The method of manufacturing according to claim 1, characterized in that: the initiator comprises potassium persulfate.
5. The method of manufacturing according to claim 1, characterized in that: the protective gas includes nitrogen.
6. A methylol urea-PTGE-carboxymethyl cellulose freeze-proof, water-proof and sand-fixing material prepared by the preparation method of any one of claims 1 to 5.
7. The methylol urea-PTGE-carboxymethyl cellulose antifreezing water-resistant sand-fixing material according to claim 6, wherein: the water permeability coefficient of the methylol urea-PTGE-carboxymethyl cellulose antifreezing water-resistant sand-fixing material is 5 multiplied by 10 -4 cm/s ~ 1.5 × 10-3 cm/s, the compressive strength of a sand-fixing sample is 4-6 MPa, and after curing 8-h, the bonding strength of the sand-fixing sample at-210-196 ℃ liquid nitrogen temperature is 3-7 MPa.
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| CN112175624A (en) * | 2020-10-27 | 2021-01-05 | 中国科学院西北生态环境资源研究院 | Nano-adhesive substrate for sand fixation, nano-biomaterial and sand fixation method |
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| EP3027233A4 (en) * | 2013-08-01 | 2017-04-05 | Intellisiv Ltd | Hydrogel fibers and preparation thereof |
| CN114437730B (en) * | 2021-12-31 | 2024-01-30 | 中北大学 | Urea aldehyde group biodegradable polymer sand-fixing material with functions of nutrient slow and controlled release, water absorption and water retention |
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| CN107417393A (en) * | 2017-07-31 | 2017-12-01 | 中北大学 | A kind of preparation of cellulose base multiple nutrient macromolecule slow-release or control-release fertilizer |
| CN112175624A (en) * | 2020-10-27 | 2021-01-05 | 中国科学院西北生态环境资源研究院 | Nano-adhesive substrate for sand fixation, nano-biomaterial and sand fixation method |
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