CN113754988A - Preparation process of imitated cement with high flexural modulus - Google Patents
Preparation process of imitated cement with high flexural modulus Download PDFInfo
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Abstract
The invention discloses a preparation process of high-flexural modulus imitated cement, which comprises the following raw materials in parts by weight: 30-50 parts of limestone, 5-10 parts of clay, 10-15 parts of silicon micropowder, 30-60 parts of modified resin and 6-12 parts of reinforcing liquid; contain a plurality of many carbon long chains on this modified resin molecule, make the modified resin toughness who prepares out promote, contain sulfone class structure on the molecular chain simultaneously, make the antioxidant capacity of resin promote, and then the life of imitative cement has been strengthened, the benzoxazine structure on the molecular chain makes the heat-resisting effect of imitative cement of preparing better simultaneously, amino on this reinforcing particle can react with remaining epoxy on the modified resin molecule, make reinforcing particle and modified resin graft, the combined material of carbon fiber and graphite alkene, good mechanical properties has, and then make the crooked mill volume of imitative cement further promote.
Description
Technical Field
The invention relates to the technical field of high-strength material preparation, in particular to a preparation process of high-flexural-modulus imitated cement.
Background
Cement concrete is the civil engineering material which is most widely applied at present, but is also a typical quasi-brittle material. The high brittleness is an inherent defect of cement concrete, and is one of the main reasons for cracking a concrete structure, causing structural failure and deteriorating durability. Improving the brittleness and improving the toughness of cement concrete has long been a key point and a difficulty which are concerned by the academic and engineering circles.
The current technical measures for improving the brittleness of concrete mainly comprise fiber toughening, polymer emulsion modification and the like. The fiber toughening technology has the advantages that the short and fine fibers in the concrete and a cement matrix form a good bonding effect, and when the set cement is damaged, the tensile strength and the modulus are high, and the effect of bridging the set cement is utilized, so that crack expansion is delayed, and the toughness of the concrete is improved. At present, steel fibers, organic fibers and the like are most widely applied, but the fiber has poor dispersibility and compatibility in a cement-stone matrix, the steel fibers have the problems of corrosion in a humid environment, economic cost and the like, and the wide application of the fiber toughened concrete is limited.
The problem of large concrete brittleness caused by the appearance of the imitation cement is solved to a certain extent, high polymer materials can be added in the preparation of the imitation cement, part of the high polymer materials are expensive and low in price, ageing is easy to occur, the high-temperature resistant effect is general, the mechanical property of the high polymer materials is poor, and the problem of large concrete brittleness caused by the preparation of the imitation cement cannot be well solved.
Disclosure of Invention
The invention aims to provide a preparation process of imitated cement with high flexural modulus, which solves the problems that a cement material is low in flexural modulus and easy to break after being extruded by external force at the present stage, and simultaneously avoids the problems of short service life and poor high-temperature resistance effect of the existing imitated cement through modified resin and reinforcing liquid.
The purpose of the invention can be realized by the following technical scheme:
the preparation process of the imitated cement with high flexural modulus comprises the following raw materials in parts by weight: 30-50 parts of limestone, 5-10 parts of clay, 10-15 parts of silicon micropowder, 30-60 parts of modified resin and 6-12 parts of reinforcing liquid;
the imitation cement is prepared by uniformly blending the raw materials and then pressing at the temperature of 60-70 ℃.
Further, the modified resin is prepared by the following steps:
step A1: adding pyromellitic dianhydride, 4' -diaminodiphenyl sulfone and N, N-dimethylformamide into a reaction kettle, stirring at the rotation speed of 150-200r/min and the temperature of 0-5 ℃ for 10-15min, heating to the temperature of 20-25 ℃, reacting for 2-3h to obtain an intermediate 1, uniformly mixing the intermediate 1, paraformaldehyde, p-aminophenol and N, N-dimethylformamide, reacting at the rotation speed of 200-300r/min and the temperature of 100-110 ℃ for 3-5h, adjusting the pH value of a reaction solution to be neutral to obtain an intermediate 2, adding chlorobenzene into the reaction kettle, stirring and introducing phosgene at the rotation speed of 200-300r/min and the temperature of 20-25 ℃, adding the intermediate 2, and reacting for 3-5h at the temperature of 90-100 ℃ to obtain an intermediate 3;
the reaction process is as follows:
step A2: adding 2, 2-diphenylpropane into a reaction kettle, stirring and dropwise adding mixed acid under the conditions that the rotation speed is 120-one-function drugs at 150r/min and the temperature is 30-35 ℃, heating to 50-55 ℃ after dropwise adding is finished, reacting for 1-2h to obtain an intermediate 4, uniformly mixing the intermediate 4, dibenzoyl peroxide and triethanolamine, heating to 60-70 ℃, introducing chlorine gas, reacting for 3-4h to obtain an intermediate 5, dissolving the intermediate 5 in xylene, adding a sodium carbonate aqueous solution, and reacting for 4-6h under the conditions that the rotation speed is 200-one-function drugs at 300r/min and the temperature is 90-95 ℃ to obtain an intermediate 6;
the reaction process is as follows:
step A3: uniformly mixing the intermediate 6, hexadecanoic acid, ether and copper sulfate, carrying out reflux reaction for 3-5h at the temperature of 90-100 ℃, adding tin powder and concentrated hydrochloric acid, uniformly mixing, carrying out reaction for 30-50min at the rotation speed of 200r/min and the temperature of 95-100 ℃, adjusting the pH value of a reaction solution to 9-10 to obtain an intermediate 7, adding epoxy resin E-51, the intermediate 7 and N, N-dimethylformamide into a reaction kettle, carrying out reaction for 1.5-2h at the rotation speed of 200r/min and the temperature of 75-85 ℃, heating to the temperature of 120 f/min and 130 ℃, continuing to carry out reaction for 2-4h, adding the intermediate 3, continuing to react for 1-1.5h, dropwise adding dibutyltin dilaurate, carrying out reaction for 1-2h, to obtain the modified resin.
The reaction process is as follows:
further, the molar ratio of the pyromellitic dianhydride to the 4,4' -diaminodiphenyl sulfone in the step A1 is 1:2, the molar ratio of the intermediate 1 to the paraformaldehyde to the p-aminophenol is 1:2:2, and the molar ratio of the chlorobenzene to the phosgene to the intermediate 2 is 20mL to 0.02mol to 0.01 mol.
Further, the mass ratio of the 2, 2-diphenylpropane to the mixed acid in the step A2 is 2:5, the mixed acid is formed by mixing concentrated nitric acid with the mass fraction of 68% and concentrated sulfuric acid with the mass fraction of 98% in a volume ratio of 9:10, the mass ratio of the intermediate 4, dibenzoyl peroxide, triethanolamine and chlorine is 1mol:3g:0.5g:1mol, the mass ratio of the intermediate 5 to the sodium carbonate aqueous solution is 1g:6mL, and the mass fraction of the sodium carbonate aqueous solution is 10%.
Further, the intermediate 6, the hexadecanoic acid, the tin powder and the concentrated hydrochloric acid in the step A3 are used in a ratio of 5g to 3.6 to 8g to 20mL, and the epoxy resin E-51, the intermediate 7, the intermediate 3 and the dibutyl tin dilaurate are used in a ratio of 10mol to 2mol to 40mol to 5 mL.
Further, the enhancing liquid is prepared by the following steps:
step B1: adding graphite and sodium nitrate into concentrated sulfuric acid, stirring for 25-30min at the rotation speed of 200-300r/min and the temperature of 0-3 ℃, adding potassium permanganate, continuing to stir for 1.5-2h, heating to 40-50 ℃, reacting for 2-3h, adding deionized water, continuing to stir for 30-40min at the temperature of 95-98 ℃, adding hydrogen peroxide until the reaction liquid is bright yellow, washing for 3 times with a hydrochloric acid solution, washing with distilled water to neutrality, and centrifugally drying to obtain graphene oxide;
step B2: adding carbon fibers into a nitric acid solution, carrying out ultrasonic treatment for 2-3h under the condition of frequency of 40-50kHz, filtering to remove filtrate, dispersing a filter cake into deionized water, adding sodium borohydride, and reacting for 1-1.5h under the conditions of rotation speed of 200-300r/min and temperature of 25-30 ℃ to obtain hydroxylated carbon fibers;
step B3: dispersing hydroxylated carbon fibers in deionized water, adding gamma-aminopropyltriethoxysilane, stirring for 3-5h at the rotation speed of 150-200r/min at the temperature of 60-70 ℃ and under the condition that the pH value is 9-10, adding graphene oxide and 1-hydroxybenzotriazole, continuously reacting for 2-3h, filtering to remove filtrate to obtain reinforcing particles, and dispersing the reinforcing particles in the deionized water to obtain a reinforcing liquid.
Further, the using amount ratio of the graphite, the sodium nitrate, the concentrated sulfuric acid, the potassium permanganate and the deionized water in the step B1 is 5g:3g:125mL:20g:230 mL.
Further, the using amount ratio of the carbon fiber, the nitric acid solution and the sodium borohydride in the step B2 is 1g to 5mL to 1.5g, and the mass fraction of the nitric acid solution is 10%.
Further, the mass ratio of the hydroxylated carbon fiber, the gamma-aminopropyltriethoxysilane, the graphene oxide and the 1-hydroxybenzotriazole in the step B3 is 5:0.15:0.5:0.2, and the mass ratio of the reinforcing particles to the deionized water is 1g:5 mL.
The invention has the beneficial effects that: the invention prepares modified resin and reinforcing liquid in the process of preparing high bending modulus imitation cement, the modified resin takes pyromellitic dianhydride and 4,4' -diaminodiphenyl sulfone as raw materials to react to prepare an intermediate 1, the intermediate 1 reacts with p-aminophenol to prepare an intermediate 2, phosgene is used to treat the intermediate 2 to convert amino on the intermediate 2 into isocyanate group to prepare an intermediate 3, 2-diphenylpropane is nitrated to prepare an intermediate 4, the intermediate 4 is chlorinated to prepare an intermediate 5, the intermediate 5 is hydrolyzed to prepare an intermediate 6, the intermediate 6 and hexadecanoic acid are esterified and then are subjected to reduction reaction to prepare an intermediate 7, the intermediate 7 reacts with epoxy resin E-51 to react the amino of the intermediate 7 with epoxy group at one end of the epoxy resin E-51, after the intermediate 3 is keyed in, the isocyanate group on the intermediate 3 reacts with the alcoholic hydroxyl group on the adjacent molecular chain to prepare modified resin, the molecules of the modified resin contain a plurality of multi-carbon long chains, so that the toughness of the prepared modified resin is improved, meanwhile, the molecular chains contain sulfone structures, so that the oxidation resistance of the resin is improved, the service life of the imitation cement is further prolonged, meanwhile, the benzoxazine structures on the molecular chains ensure that the prepared imitation cement has better heat-resistant effect, the reinforcing liquid takes graphite as a raw material to carry out oxidation treatment to prepare graphene oxide, then the carbon fiber is treated to hydroxylate the carbon fiber, then the gamma-aminopropyltriethoxysilane is hydrolyzed and hydroxylated to graft according to the fiber, so that a large number of amino groups are attached to the surface of the carbon fiber, then the graphene oxide is added, and the carboxyl on the surface of the graphene oxide and part of the amino groups on the carbon fiber are subjected to dehydration condensation, the reinforced particles are prepared and then dispersed in deionized water to prepare a reinforced liquid, amino groups on the reinforced particles can react with residual epoxy groups on modified resin molecules, so that the reinforced particles are grafted with the modified resin, and the composite material of the carbon fiber and the graphene has good mechanical property, so that the bending grinding amount of the imitation cement is further improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation process of the imitated cement with high flexural modulus comprises the following raw materials in parts by weight: 30 parts of limestone, 5 parts of clay, 10 parts of silica micropowder, 30 parts of modified resin and 6 parts of reinforcing liquid;
the imitation cement is prepared by uniformly blending the raw materials and then performing compression molding at the temperature of 60 ℃.
The modified resin is prepared by the following steps:
step A1: adding pyromellitic dianhydride, 4' -diaminodiphenyl sulfone and N, N-dimethylformamide into a reaction kettle, stirring for 10min at the rotation speed of 150r/min and the temperature of 0 ℃, heating to the temperature of 20 ℃, reacting for 2h to obtain an intermediate 1, uniformly mixing the intermediate 1, paraformaldehyde, p-aminophenol and N, N-dimethylformamide, reacting for 3h at the rotation speed of 200r/min and the temperature of 100 ℃, adjusting the pH value of a reaction solution to be neutral to obtain an intermediate 2, adding chlorobenzene into the reaction kettle, stirring and introducing phosgene at the rotation speed of 200r/min and the temperature of 20 ℃, adding the intermediate 2, and reacting for 3h at the temperature of 90 ℃ to obtain an intermediate 3;
step A2: adding 2, 2-diphenylpropane into a reaction kettle, stirring and dropwise adding mixed acid under the conditions of the rotating speed of 120r/min and the temperature of 30 ℃, heating to 50 ℃ after dropwise adding, reacting for 1h to obtain an intermediate 4, uniformly mixing the intermediate 4, dibenzoyl peroxide and triethanolamine, heating to 60 ℃, introducing chlorine, reacting for 3h to obtain an intermediate 5, dissolving the intermediate 5 in xylene, adding a sodium carbonate aqueous solution, and reacting for 4h under the conditions of the rotating speed of 200r/min and the temperature of 90 ℃ to obtain an intermediate 6;
step A3: uniformly mixing the intermediate 6, hexadecanoic acid, diethyl ether and copper sulfate, carrying out reflux reaction for 3 hours at the temperature of 90 ℃, adding tin powder and concentrated hydrochloric acid, uniformly mixing, carrying out reaction for 30 minutes at the rotation speed of 150r/min and the temperature of 95 ℃, adjusting the pH value of a reaction solution to 9 to prepare an intermediate 7, adding epoxy resin E-51, the intermediate 7, N-dimethylformamide into a reaction kettle, carrying out reaction for 1.5 hours at the rotation speed of 200r/min and the temperature of 75 ℃, heating to the temperature of 120 ℃, continuing to react for 2 hours, adding the intermediate 3, continuing to react for 1 hour, dropwise adding dibutyltin dilaurate, and carrying out reaction for 1 hour to prepare the modified resin.
The reinforcing liquid is prepared by the following steps:
step B1: adding graphite and sodium nitrate into concentrated sulfuric acid, stirring for 25min at the rotation speed of 200r/min and the temperature of 0 ℃, adding potassium permanganate, continuing to stir for 1.5h, heating to 40 ℃, reacting for 2h, adding deionized water, continuing to stir for 30min at the temperature of 95 ℃, adding hydrogen peroxide until the reaction solution is bright yellow, washing for 3 times with a hydrochloric acid solution, washing with distilled water to be neutral, and centrifugally drying to obtain graphene oxide;
step B2: adding carbon fibers into a nitric acid solution, carrying out ultrasonic treatment for 2 hours under the condition of 40kHz frequency, filtering to remove filtrate, dispersing filter cakes into deionized water, adding sodium borohydride, and reacting for 1 hour under the conditions of 200r/min of rotation speed and 25 ℃ to obtain hydroxylated carbon fibers;
step B3: dispersing hydroxylated carbon fibers in deionized water, adding gamma-aminopropyltriethoxysilane, stirring for 3 hours at the rotation speed of 150r/min, the temperature of 60 ℃ and the pH value of 9, adding graphene oxide and 1-hydroxybenzotriazole, continuously reacting for 2 hours, filtering to remove filtrate to obtain reinforcing particles, and dispersing the reinforcing particles in deionized water to obtain a reinforcing liquid.
Example 2
The preparation process of the imitated cement with high flexural modulus comprises the following raw materials in parts by weight: 40 parts of limestone, 8 parts of clay, 13 parts of silica micropowder, 50 parts of modified resin and 10 parts of reinforcing liquid;
the imitation cement is prepared by uniformly blending the raw materials and then performing compression molding at the temperature of 65 ℃.
The modified resin is prepared by the following steps:
step A1: adding pyromellitic dianhydride, 4' -diaminodiphenyl sulfone and N, N-dimethylformamide into a reaction kettle, stirring for 13min at the rotation speed of 180r/min and the temperature of 3 ℃, heating to the temperature of 23 ℃, reacting for 2.5h to obtain an intermediate 1, uniformly mixing the intermediate 1, paraformaldehyde, p-aminophenol and N, N-dimethylformamide, reacting for 4h at the rotation speed of 200r/min and the temperature of 105 ℃, adjusting the pH value of a reaction solution to be neutral to obtain an intermediate 2, adding chlorobenzene into the reaction kettle, stirring and introducing phosgene at the rotation speed of 300r/min and the temperature of 23 ℃, adding the intermediate 2, and reacting for 4h at the temperature of 95 ℃ to obtain an intermediate 3;
step A2: adding 2, 2-diphenylpropane into a reaction kettle, stirring and dropwise adding mixed acid under the conditions that the rotating speed is 150r/min and the temperature is 33 ℃, heating to 53 ℃ after dropwise adding is finished, reacting for 1.5h to obtain an intermediate 4, uniformly mixing the intermediate 4, dibenzoyl peroxide and triethanolamine, heating to 65 ℃, introducing chlorine, reacting for 3.5h to obtain an intermediate 5, dissolving the intermediate 5 in xylene, adding a sodium carbonate aqueous solution, and reacting for 5h under the conditions that the rotating speed is 300r/min and the temperature is 93 ℃ to obtain an intermediate 6;
step A3: uniformly mixing the intermediate 6, hexadecanoic acid, diethyl ether and copper sulfate, carrying out reflux reaction for 4 hours at the temperature of 95 ℃, adding tin powder and concentrated hydrochloric acid, uniformly mixing, carrying out reaction for 40 minutes at the rotation speed of 180r/min and the temperature of 98 ℃, adjusting the pH value of a reaction solution to 9 to prepare an intermediate 7, adding epoxy resin E-51, the intermediate 7, N-dimethylformamide into a reaction kettle, carrying out reaction for 2 hours at the rotation speed of 300r/min and the temperature of 80 ℃, heating to 125 ℃, continuing to react for 3 hours, adding the intermediate 3, continuing to react for 1.3 hours, dropwise adding dibutyltin dilaurate, and carrying out reaction for 1.5 hours to prepare the modified resin.
The reinforcing liquid is prepared by the following steps:
step B1: adding graphite and sodium nitrate into concentrated sulfuric acid, stirring for 28min at the rotation speed of 300r/min and the temperature of 2 ℃, adding potassium permanganate, continuously stirring for 1.8h, heating to 45 ℃, reacting for 2.5h, adding deionized water, continuously stirring for 35min at the temperature of 96 ℃, adding hydrogen peroxide until the reaction solution is bright yellow, washing for 3 times with a hydrochloric acid solution, washing with distilled water to be neutral, and centrifugally drying to obtain graphene oxide;
step B2: adding carbon fibers into a nitric acid solution, carrying out ultrasonic treatment for 2.5h under the condition of the frequency of 45kHz, filtering to remove filtrate, dispersing a filter cake into deionized water, adding sodium borohydride, and reacting for 1.3h under the conditions of the rotating speed of 300r/min and the temperature of 28 ℃ to obtain hydroxylated carbon fibers;
step B3: dispersing hydroxylated carbon fibers in deionized water, adding gamma-aminopropyltriethoxysilane, stirring for 4 hours at the rotation speed of 180r/min and at the temperature of 65 ℃ and under the condition of pH value of 10, adding graphene oxide and 1-hydroxybenzotriazole, continuously reacting for 2.5 hours, filtering to remove filtrate to obtain reinforcing particles, and dispersing the reinforcing particles in deionized water to obtain a reinforcing liquid.
Example 3
The preparation process of the imitated cement with high flexural modulus comprises the following raw materials in parts by weight: 50 parts of limestone, 10 parts of clay, 15 parts of silica micropowder, 60 parts of modified resin and 12 parts of reinforcing liquid;
the imitation cement is prepared by uniformly blending the raw materials and then performing compression molding at the temperature of 70 ℃.
The modified resin is prepared by the following steps:
step A1: adding pyromellitic dianhydride, 4' -diaminodiphenyl sulfone and N, N-dimethylformamide into a reaction kettle, stirring for 15min at the rotation speed of 200r/min and the temperature of 5 ℃, heating to the temperature of 25 ℃, reacting for 3h to obtain an intermediate 1, uniformly mixing the intermediate 1, paraformaldehyde, p-aminophenol and N, N-dimethylformamide, reacting for 5h at the rotation speed of 300r/min and the temperature of 110 ℃, adjusting the pH value of a reaction solution to be neutral to obtain an intermediate 2, adding chlorobenzene into the reaction kettle, stirring and introducing phosgene at the rotation speed of 300r/min and the temperature of 25 ℃, adding the intermediate 2, and reacting for 5h at the temperature of 100 ℃ to obtain an intermediate 3;
step A2: adding 2, 2-diphenylpropane into a reaction kettle, stirring and dropwise adding mixed acid under the conditions that the rotating speed is 150r/min and the temperature is 35 ℃, heating to 55 ℃ after dropwise adding is finished, reacting for 2 hours to obtain an intermediate 4, uniformly mixing the intermediate 4, dibenzoyl peroxide and triethanolamine, heating to 70 ℃, introducing chlorine, reacting for 4 hours to obtain an intermediate 5, dissolving the intermediate 5 in xylene, adding a sodium carbonate aqueous solution, and reacting for 6 hours under the conditions that the rotating speed is 300r/min and the temperature is 95 ℃ to obtain an intermediate 6;
step A3: uniformly mixing the intermediate 6, hexadecanoic acid, diethyl ether and copper sulfate, carrying out reflux reaction for 5 hours at the temperature of 100 ℃, adding tin powder and concentrated hydrochloric acid, uniformly mixing, reacting for 50 minutes at the rotation speed of 200r/min and the temperature of 100 ℃, adjusting the pH value of a reaction solution to 10 to prepare an intermediate 7, adding epoxy resin E-51, the intermediate 7, N-dimethylformamide into a reaction kettle, reacting for 2 hours at the rotation speed of 300r/min and the temperature of 85 ℃, heating to the temperature of 130 ℃, continuing to react for 4 hours, adding an intermediate 3, continuing to react for 1.5 hours, dropwise adding dibutyltin dilaurate, and reacting for 2 hours to prepare the modified resin.
The reinforcing liquid is prepared by the following steps:
step B1: adding graphite and sodium nitrate into concentrated sulfuric acid, stirring for 30min at the rotation speed of 300r/min and the temperature of 3 ℃, adding potassium permanganate, continuously stirring for 2h, heating to 50 ℃, reacting for 3h, adding deionized water, continuously stirring for 40min at the temperature of 98 ℃, adding hydrogen peroxide until the reaction solution is bright yellow, washing for 3 times with a hydrochloric acid solution, washing to be neutral with distilled water, and centrifugally drying to obtain graphene oxide;
step B2: adding carbon fibers into a nitric acid solution, carrying out ultrasonic treatment for 3 hours under the condition of 50kHz, filtering to remove filtrate, dispersing filter cakes into deionized water, adding sodium borohydride, and reacting for 1.5 hours under the conditions of 300r/min of rotation speed and 30 ℃ to prepare hydroxylated carbon fibers;
step B3: dispersing hydroxylated carbon fibers in deionized water, adding gamma-aminopropyltriethoxysilane, stirring for 5 hours at the rotation speed of 200r/min, the temperature of 70 ℃ and the pH value of 10, adding graphene oxide and 1-hydroxybenzotriazole, continuously reacting for 3 hours, filtering to remove filtrate to obtain reinforcing particles, and dispersing the reinforcing particles in deionized water to obtain a reinforcing liquid.
Comparative example 1
This comparative example compared with example 1, the modified resin was replaced with epoxy resin E-51, and the procedure was the same.
Comparative example 2
This comparative example compares to example 1 without the addition of enhancing fluid and the rest of the procedure is the same.
Comparative example 3
The comparative example is a cement material disclosed in Chinese patent CN 109626901A.
The cement materials prepared in examples 1-3 and comparative examples 1-3 were tested for elastic modulus according to the standard of GB/T50081-2019, and after artificial aging for 500h, the elastic modulus was tested, and the results are shown in the following table;
from the above table, it can be seen that the elastic modulus of the simulated cement prepared in the embodiments 1-3 is 48.92-50.12GPa, and after artificial aging for 500h, the elastic modulus is still not reduced, the simulated cement material prepared by the invention has good mechanical properties, and meanwhile, the performance is not reduced after long-term use, and different from the traditional simulated cement, the high temperature resistant effect is good, and the service life of the simulated cement is prolonged.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (8)
1. A preparation process of imitated cement with high flexural modulus is characterized by comprising the following steps: the waterproof mud comprises the following raw materials in parts by weight: 30-50 parts of limestone, 5-10 parts of clay, 10-15 parts of silicon micropowder, 30-60 parts of modified resin and 6-12 parts of reinforcing liquid;
the imitation cement is prepared by uniformly blending the raw materials and then pressing the mixture;
the modified resin is prepared by the following steps:
step A1: mixing pyromellitic dianhydride, 4' -diaminodiphenyl sulfone and N, N-dimethylformamide, heating for reaction to prepare an intermediate 1, uniformly mixing the intermediate 1, paraformaldehyde, p-aminophenol and N, N-dimethylformamide for reaction, adjusting the pH value of a reaction solution to be neutral to prepare an intermediate 2, adding chlorobenzene into a reaction kettle, stirring, introducing phosgene, adding the intermediate 2, and reacting to prepare an intermediate 3;
step A2: adding 2, 2-diphenyl propane into a reaction kettle, stirring and dropwise adding mixed acid, heating for reaction after dropwise adding is finished to obtain an intermediate 4, uniformly mixing the intermediate 4, dibenzoyl peroxide and triethanolamine, heating and introducing chlorine gas for reaction to obtain an intermediate 5, dissolving the intermediate 5 in xylene, adding a sodium carbonate aqueous solution, and reacting to obtain an intermediate 6;
step A3: mixing and refluxing the intermediate 6, hexadecanoic acid, ether and copper sulfate, adding tin powder and concentrated hydrochloric acid for reaction, adjusting the pH value of a reaction solution to obtain an intermediate 7, adding epoxy resin E-51, the intermediate 7 and N, N-dimethylformamide into a reaction kettle, heating for continuous reaction after the reaction is carried out, adding the intermediate 3, dropwise adding dibutyltin dilaurate after the continuous reaction is carried out, and carrying out the reaction to obtain the modified resin.
2. The process for preparing the imitated cement with high flexural modulus according to claim 1, which is characterized in that: the using molar ratio of the pyromellitic dianhydride to the 4,4' -diaminodiphenyl sulfone in the step A1 is 1:2, the using molar ratio of the intermediate 1, the paraformaldehyde and the p-aminophenol is 1:2:2, and the using ratio of the chlorobenzene to the phosgene is 20mL to 0.02mol to 0.01 mol.
3. The process for preparing the imitated cement with high flexural modulus according to claim 1, which is characterized in that: the mass ratio of the 2, 2-diphenylpropane to the mixed acid in the step A2 is 2:5, the mass ratio of the intermediate 4, the dibenzoyl peroxide, the triethanolamine and the chlorine is 1mol:3g:0.5g:1mol, and the mass ratio of the intermediate 5 to the sodium carbonate aqueous solution is 1g:6 mL.
4. The process for preparing the imitated cement with high flexural modulus according to claim 1, which is characterized in that: the dosage ratio of the intermediate 6, the hexadecanoic acid, the tin powder and the concentrated hydrochloric acid in the step A3 is 5g:3.6:8g:20mL, and the dosage ratio of the epoxy resin E-51, the intermediate 7, the intermediate 3 and the dibutyl tin dilaurate is 10mol:2mol:40mol:5 mL.
5. The process for preparing the imitated cement with high flexural modulus according to claim 1, which is characterized in that: the reinforcing liquid is prepared by the following steps:
step B1: adding graphite and sodium nitrate into concentrated sulfuric acid, stirring, adding potassium permanganate, continuing stirring, heating for reaction, adding deionized water, continuing stirring, adding hydrogen peroxide until the reaction solution is bright yellow, washing with a hydrochloric acid solution for 3 times, washing with distilled water to be neutral, and centrifugally drying to obtain graphene oxide;
step B2: adding carbon fibers into a nitric acid solution, carrying out ultrasonic treatment, filtering to remove filtrate, dispersing a filter cake into deionized water, adding sodium borohydride, and reacting to obtain hydroxylated carbon fibers;
step B3: dispersing hydroxylated carbon fibers in deionized water, adding gamma-aminopropyltriethoxysilane for reaction, adding graphene oxide and 1-hydroxybenzotriazole for continuous reaction, filtering to remove filtrate to obtain reinforcing particles, and dispersing the reinforcing particles in deionized water to obtain a reinforcing liquid.
6. The process for preparing the imitated cement with high flexural modulus as claimed in claim 5, wherein the process comprises the following steps: the using amount ratio of the graphite, the sodium nitrate, the concentrated sulfuric acid, the potassium permanganate and the deionized water in the step B1 is 5g to 3g to 125mL to 20g to 230 mL.
7. The process for preparing the imitated cement with high flexural modulus as claimed in claim 5, wherein the process comprises the following steps: the using amount ratio of the carbon fiber, the nitric acid solution and the sodium borohydride in the step B2 is 1g to 5mL to 1.5 g.
8. The process for preparing the imitated cement with high flexural modulus as claimed in claim 5, wherein the process comprises the following steps: the mass ratio of the hydroxylated carbon fiber, the gamma-aminopropyltriethoxysilane, the graphene oxide and the 1-hydroxybenzotriazole in the step B3 is 5:0.15:0.5:0.2, and the mass ratio of the reinforcing particles to the deionized water is 1g:5 mL.
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