Cement containing sulfonic acid cellulose and preparation method thereof

Abstract

The invention relates to the technical field of building materials, and discloses cement containing sulfonic acid cellulose and a preparation method thereof.The preparation method includes the steps that gypsum, coal gangue and Portland cement clinker are smashed and added into a concrete mixer to be stirred, then sulfonic acid cellulose, kieselguhr, calcium formate and quaternary ammonium salt modified polyurethane are added into the concrete mixer to be stirred, and the cement containing sulfonic acid cellulose is obtained; the cement containing the sulfonic acid cellulose is obtained. The cement containing sulfonic acid cellulose provided by the invention has better crack resistance, durability and good mechanical properties.

Description

Technical Field

[0001] The present invention relates to the technical field of building materials, and specifically to a cement containing sulfonated cellulose and a preparation method thereof. Background Art

[0002] As an important building material, cement is widely used in many engineering fields such as construction, roads, and bridges. However, traditional cement has certain limitations in performance, such as the need to further improve crack resistance and durability. Therefore, how to avoid this phenomenon is the key to solving the problem. For example, Patent CN112957524B discloses a bone cement and its preparation method and application. The bone cement includes a powder and a liquid. The powder includes polymethyl methacrylate, esterified starch, initiator, and developer, and the liquid includes methyl methacrylate monomer, accelerator, and inhibitor. This cement has good mechanical properties, but its crack resistance needs to be improved. Summary of the Invention

[0003] (I) Technical Problems to be Solved Aiming at the deficiencies of the prior art, the present invention provides a cement containing sulfonated cellulose and a preparation method thereof, which has good crack resistance, durability, and good mechanical properties.

[0004] (II) Technical Solutions To achieve the above object, the present invention provides the following technical solutions: A cement containing sulfonated cellulose, comprising the following weight components: 1-2 parts by weight of sulfonated cellulose, 10-16 parts by weight of gypsum, 6-10 parts by weight of diatomite, 9-14 parts by weight of coal gangue, 60-70 parts by weight of Portland cement clinker, 1-3 parts by weight of calcium formate, and 2-4 parts by weight of quaternary ammonium salt modified polyurethane.

[0005] Further, the preparation method of the sulfonated cellulose is as follows: Add 1.9-2.1 g of nanocrystalline cellulose to 90-100 mL of a 5% sodium hydroxide solution, put it into an ultrasonic crusher, ultrasonicate for 15-18 min, then stir at 45-50 °C for 2-4 h. Then add 2.3-3.1 g of 1,4-butanesultone thereto, stir and react at 55-60 °C for 6-7 h. After completion, adjust the pH of the solution to 1-2 with 5% HCl, then dialyze and dry to obtain sulfonated cellulose.

[0006] Further, the preparation method of the quaternary ammonium salt modified polyurethane is as follows: S1. Add 4-[N,N-bis(2-hydroxyethyl)amino]benzaldehyde and N,N-dimethylethylenediamine to an N,N-dimethylformamide solvent, stir and mix, heat up and react for 4-6 h. After completion, carry out reduced pressure distillation, washing, and drying to obtain Intermediate 1; S2. Add toluene diisocyanate and polytetrahydrofuran diol into a reaction kettle, then add dibutyltin dilaurate. Under a nitrogen atmosphere, carry out prepolymerization at a temperature of 70 - 90 °C for 2 - 3 h. Then add intermediate 1 and stir to carry out a chain extension reaction, react at 50 - 60 °C for 20 - 25 min. After the reaction ends, cool naturally to obtain tertiary amino polyurethane; S3. Add tertiary amino polyurethane and allyl-1,3-sultone into N,N-dimethylformamide solvent, and then continue to add a sodium hydroxide solution with a mass fraction of 3 - 6%. React at 50 - 55 °C for 4 - 7 h. After completion, perform rotary evaporation and filtration to obtain quaternary ammonium salt modified polyurethane.

[0007] Furthermore, in S1, the dosage ratio of 4-[N,N-bis(2-hydroxyethyl)amino]benzaldehyde, N,N-dimethylethylenediamine, and N,N-dimethylformamide is 2.31 - 2.35 g:0.82 - 0.85 g:50 - 60 mL.

[0008] Furthermore, in S1, the reaction temperature is 65 - 80 °C.

[0009] Furthermore, in S2, the mass ratio of toluene diisocyanate, polytetrahydrofuran diol, dibutyltin dilaurate, and intermediate 1 is 0.8 - 0.9 g:1.22 - 1.26 g:0.01 - 0.02 g:0.4 - 0.5 g.

[0010] Furthermore, in S3, the dosage ratio of N,N-dimethylformamide, tertiary amino polyurethane, and allyl-1,3-sultone is 45 - 55 mL:1.13 - 1.34 g:4.5 - 4.7 g.

[0011] Furthermore, the preparation method of the cement containing sulfonic acid cellulose is as follows: Crush gypsum, coal gangue, and Portland cement clinker, ball mill to a particle size of 50 - 80 μm, add them into a concrete mixer, stir for 5 - 10 min, and then add sulfonic acid cellulose, diatomite, calcium formate, and quaternary ammonium salt modified polyurethane into the stirrer and stir for 10 - 15 min to obtain the cement containing sulfonic acid cellulose.

[0012] (III) Beneficial technical effects In the present invention, gypsum, coal gangue, and Portland cement clinker are crushed, added into a concrete mixer and stirred, and then sulfonic acid cellulose, diatomite, calcium formate, and quaternary ammonium salt modified polyurethane are added into the stirrer and stirred to obtain the cement containing sulfonic acid cellulose.

[0013] The sodium sulfonate groups in quaternary ammonium salt modified polyurethane and sulfonic acid cellulose prevent the formation of flocculation structures between cement particles through their steric hindrance effect and electrostatic repulsion. Without changing the workability of concrete, the water consumption can be reduced, and the strength and durability of cement can be improved, achieving a good water reducing effect together. The polyurethane and quaternary ammonium salt in quaternary ammonium salt modified polyurethane can improve the mechanical properties and crack resistance of cement. The cellulose in sulfonic acid cellulose-containing can form a three-dimensional spatial network structure in cement, which interweaves with other components in cement and fills the pores in cement, enhancing the toughness and crack resistance of cement. Brief Description of the Drawings

[0014] Figure 1 is the reaction equation of Intermediate 1.

[0015] Figure 2 is the NMR spectrum of Intermediate 1. Detailed Embodiments

[0016] To make the objectives, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below. Obviously, the described embodiments are some, but not all, of the embodiments of the present invention. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0017] To better understand the above technical solutions, the above technical solutions will be described in detail below in conjunction with the drawings of the specification and specific embodiments.

[0018] Example 1 S1. Add 2.31 g of 4-[N,N-bis(2-hydroxyethyl)amino]benzaldehyde and 0.82 g of N,N-dimethylethylenediamine to 50 mL of N,N-dimethylformamide solvent, stir and mix, heat up to 65 °C and react for 4 h. After completion, carry out vacuum distillation, washing, and drying to obtain Intermediate 1; S2. Add 0.8 g of toluene diisocyanate and 1.22 g of polytetrahydrofuran diol to the reaction kettle, and then add 0.01 g of dibutyltin dilaurate. Under a nitrogen atmosphere, carry out prepolymerization at a temperature of 70 °C for 2 h. Then add 0.4 g of Intermediate 1 and stir for chain extension reaction, react at 50 °C for 20 min. After the reaction is completed, cool naturally to obtain tertiary amine group polyurethane; S3. Add 1.13 g of tertiary amine group polyurethane and 4.5 g of allyl-1,3-sultone to 45 mL of N,N-dimethylformamide solvent, and then continue to add a 3% sodium hydroxide solution by mass. React at 50 °C for 4 h. After completion, carry out rotary evaporation and filtration to obtain quaternary ammonium salt modified polyurethane; S4. Add 1.9 g of nanocrystalline cellulose to 90 mL of 5% sodium hydroxide solution, place it in an ultrasonic crusher, ultrasonicate for 15 min, then stir at 45 °C for 2 h. Continue to add 2.3 g of 1,4-butanesultone and stir and react at 55 °C for 6 h. After completion, adjust the pH of the solution to 1 with 5% HCl, then dialyze and dry to obtain sulfonated cellulose; S5. Crush 10 parts by weight of gypsum, 9 parts by weight of coal gangue, and 60 parts by weight of Portland cement clinker, ball mill to a particle size of 50 μm, add to a concrete mixer, stir for 5 min, then add 1 part by weight of sulfonated cellulose, 6 parts by weight of diatomite, 1 part by weight of calcium formate, and 2 parts by weight of quaternary ammonium salt modified polyurethane to the stirrer and stir for 10 min to obtain cement containing sulfonated cellulose.

[0019] Example 2 S1. Add 2.35 g of 4-[N,N-bis(2-hydroxyethyl)amino]benzaldehyde and 0.85 g of N,N-dimethylethylenediamine to 60 mL of N,N-dimethylformamide solvent, stir and mix, heat up to 80 °C and react for 6 h. After completion, carry out vacuum distillation, wash, and dry to obtain Intermediate 1; S2. Add 0.9 g of toluene diisocyanate and 1.26 g of polytetrahydrofuran diol to a reaction kettle, then add 0.02 g of dibutyltin dilaurate, and carry out prepolymerization under a nitrogen atmosphere at a prepolymerization temperature of 90 °C for 3 h. Then add 0.5 g of Intermediate 1 and stir for chain extension reaction, react at 60 °C for 25 min. After the reaction is completed, cool naturally to obtain tertiary amino group polyurethane; S3. Add 1.34 g of tertiary amino group polyurethane and 4.7 g of allyl-1,3-sultone to 55 mL of N,N-dimethylformamide solvent, then continue to add 6% sodium hydroxide solution, react at 55 °C for 7 h. After completion, carry out rotary evaporation and filtration to obtain quaternary ammonium salt modified polyurethane; S4. Add 2.1 g of nanocrystalline cellulose to 100 mL of 5% sodium hydroxide solution, place it in an ultrasonic crusher, ultrasonicate for 18 min, then stir at 50 °C for 4 h. Continue to add 3.1 g of 1,4-butanesultone and stir and react at 60 °C for 7 h. After completion, adjust the pH of the solution to 2 with 5% HCl, then dialyze and dry to obtain sulfonated cellulose; S5. Crush 16 parts by weight of gypsum, 14 parts by weight of coal gangue, and 70 parts by weight of portland cement clinker, ball mill them to a particle size of 80 μm, add them to a concrete mixer, stir for 10 min, then add 2 parts by weight of sulfonic acid cellulose, 10 parts by weight of diatomite, 3 parts by weight of calcium formate, and 4 parts by weight of quaternary ammonium salt modified polyurethane to the stirrer, and stir for 15 min to obtain cement containing sulfonic acid cellulose.

[0020] Example 3 S1. Add 2.32 g of 4-[N,N-bis(2-hydroxyethyl)amino]benzaldehyde and 0.84 g of N,N-dimethylethylenediamine to 55 mL of N,N-dimethylformamide solvent, stir and mix, heat up to 70 °C and react for 5 h. After completion, perform vacuum distillation, washing, and drying to obtain Intermediate 1; S2. Add 0.85 g of toluene diisocyanate and 1.24 g of polytetrahydrofuran diol to a reaction kettle, then add 0.015 g of dibutyltin dilaurate, and perform prepolymerization under a nitrogen atmosphere. The prepolymerization temperature is 80 °C and the time is 2 h. Then add 0.45 g of Intermediate 1 and stir for chain extension reaction, react at 55 °C for 22 min. After the reaction is completed, cool naturally to obtain tertiary amino group polyurethane; S3. Add 1.25 g of tertiary amino group polyurethane and 4.6 g of allyl-1,3-sultone to 50 mL of N,N-dimethylformamide solvent, then continue to add a 4% sodium hydroxide solution, react at 52 °C for 5 h. After completion, perform rotary evaporation and filtration to obtain quaternary ammonium salt modified polyurethane; S4. Add 2.0 g of nanocrystalline cellulose to 95 mL of a 5% sodium hydroxide solution, place it in an ultrasonic crusher, ultrasonicate for 17 min, then stir at 48 °C for 3 h. Continue to add 2.9 g of 1,4-butanesultone and stir and react at 57 °C for 6.5 h. After completion, adjust the pH of the solution to 1 with 5% HCl, then dialyze and dry to obtain sulfonic acid cellulose; S5. Crush 13 parts by weight of gypsum, 12 parts by weight of coal gangue, and 65 parts by weight of portland cement clinker, ball mill them to a particle size of 70 μm, add them to a concrete mixer, stir for 8 min, then add 1.5 parts by weight of sulfonic acid cellulose, 8 parts by weight of diatomite, 2 parts by weight of calcium formate, and 3 parts by weight of quaternary ammonium salt modified polyurethane to the stirrer, and stir for 12 min to obtain cement containing sulfonic acid cellulose.

[0021] Example 4 S1. Add 2.31 g of 4-[N,N-bis(2-hydroxyethyl)amino]benzaldehyde and 0.82 g of N,N-dimethylethylenediamine to 50 mL of N,N-dimethylformamide solvent, stir and mix, heat up to 65 °C and react for 4 h. After completion, perform vacuum distillation, washing, and drying to obtain Intermediate 1; S2. Add 0.8 g of toluene diisocyanate and 1.22 g of polytetrahydrofuran diol to a reaction kettle, then add 0.01 g of dibutyltin dilaurate, and perform prepolymerization under a nitrogen atmosphere at a temperature of 70 °C for 2 h. Then add 0.4 g of Intermediate 1 and stir for chain extension reaction, react at 50 °C for 20 min. After the reaction is completed, cool naturally to obtain tertiary amino polyurethane; S3. Add 1.34 g of tertiary amino polyurethane and 4.7 g of allyl-1,3-sultone to 55 mL of N,N-dimethylformamide solvent, then continue to add a 6% sodium hydroxide solution by mass fraction, and react at 55 °C for 7 h. After completion, perform rotary evaporation and filtration to obtain quaternary ammonium salt modified polyurethane; S4. Add 2.0 g of nanocrystalline cellulose to 95 mL of a 5% sodium hydroxide solution by mass fraction, put it into an ultrasonic disintegrator, ultrasonicate for 17 min, then stir at 48 °C for 3 h. Continue to add 2.9 g of 1,4-butanesultone, and stir and react at 57 °C for 6.5 h. After completion, adjust the pH of the solution to 1 with 5% HCl by mass fraction, then dialyze and dry to obtain sulfonated cellulose; S5. Crush 13 parts by weight of gypsum, 12 parts by weight of coal gangue, and 65 parts by weight of Portland cement clinker, ball mill to a particle size of 70 μm, add to a concrete mixer, stir for 8 min, then add 1.5 parts by weight of sulfonated cellulose, 8 parts by weight of diatomite, 2 parts by weight of calcium formate, and 3 parts by weight of quaternary ammonium salt modified polyurethane to the stirrer, and stir for 12 min to obtain cement containing sulfonated cellulose.

[0022] Comparative Example 1 Compared with Example 4, the difference in this comparative example is that tertiary amino polyurethane is used instead of quaternary ammonium salt modified polyurethane.

[0023] Comparative Example 2 Compared with Example 4, the difference in this comparative example is that quaternary ammonium salt modified polyurethane is not added.

[0024] Comparative Example 3 Compared with Example 4, the difference in this comparative example is that sulfonated cellulose is not added.

[0025] The flexural strength and compressive strength are tested according to the GB / T17671 standard, and the test results are shown in Table 1.

[0026] Table 1: Mechanical property test.

[0027]

[0028] As can be seen from Table 1, Examples 1-4 of the present invention have better flexural strength and compressive strength compared with Comparative Examples 1-3.

[0029] The test method for the dry shrinkage rate in 90 days is as follows: First, measure the volume of the cement sample to be tested, denoted as V1. Then, place it in a room at 25°C for 90 days, and then measure the volume again, denoted as V2. Finally, calculate the dry shrinkage rate as (V1 - V2) / V1×100%.

[0030] Table 2: Shrinkage rate test.

[0031]

[0032] As can be seen from Table 1, Examples 1-4 of the present invention have better shrinkage rate compared with Comparative Examples 1-3, indicating better crack resistance.

[0033] It should be noted that in this article, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements not only includes those elements, but also includes other elements not expressly listed, or also includes elements inherent to such process, method, article or device. Without further limitation, an element defined by the statement "including one..." does not exclude the existence of another identical element in the process, method, article or device including the said element.

[0034] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements for some of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the various embodiments of the present invention.

[0035] Those skilled in the art should understand that the above are only several specific embodiments of the present invention, rather than all embodiments. It should be pointed out that many variations and improvements can be made for those of ordinary skill in the art, and all variations or improvements that do not exceed the scope of the claims should be regarded as the protection scope of the present invention.

Claims

1. A cement containing cellulose sulfonate, characterized in that: The invention comprises the following components by weight: 1-2 parts by weight of cellulose sulfonate, 10-16 parts by weight of gypsum, 6-10 parts by weight of diatomaceous earth, 9-14 parts by weight of coal gangue, 60-70 parts by weight of silicate cement clinker, 1-3 parts by weight of calcium formate and 2-4 parts by weight of quaternary ammonium salt modified polyurethane.

2. The cellulose sulfonate-containing cement according to claim 1, characterized in that The preparation method of the cellulose sulfonate is as follows: 1.9-2.1 g of nanocellulose crystals are added to 90-100 mL of a sodium hydroxide solution with a mass fraction of 5%, and the solution is put into an ultrasonic pulverizer for ultrasonication for 15-18 minutes, and then stirred at 45-50° C. for 2-4 hours, and then 2.3-3.1 g of 1,4-butanesulfonate is added thereto, and the solution is stirred at 55-60° C. for reaction for 6-7 hours, and after the solution is finished, the pH value of the solution is adjusted to 1-2 with HCl with a mass fraction of 5%, and then dialyzed and dried to obtain the cellulose sulfonate.

3. The cellulose sulfonate-containing cement according to claim 2, characterized in that The preparation method of the quaternary ammonium salt modified polyurethane is: S1. Add 4-[N,N-bis(2-hydroxyethyl)amino]benzaldehyde and N,N-dimethylethylenediamine to N,N-dimethylformamide solvent, stir and mix, heat and react for 4-6 hours, and then distill under reduced pressure, wash and dry to obtain intermediate 1; S2. Toluene diisocyanate and polytetrahydrofuran diol are added to a reaction kettle, and then dibutyltin dilaurate is added, and prepolymerization is carried out under a nitrogen atmosphere at a temperature of 70-90° C. for 2-3 hours, and then intermediate 1 is added, stirred for chain extension reaction, and reacted at 50-60° C. for 20-25 minutes. After the reaction is completed, it is cooled naturally to obtain a tertiary amino polyurethane; S3. Add tertiary amino polyurethane and acryl-1,3-sulfonate to N,N-dimethylformamide solvent, and then continue to add 3-6% by mass sodium hydroxide solution, react at 50-55°C for 4-7h, and then perform rotary distillation and filter to obtain quaternary ammonium salt modified polyurethane.

4. The cellulose sulfonate-containing cement according to claim 3, characterized in that The usage ratio of 4-[N,N-bis(2-hydroxyethyl)amino]benzaldehyde, N,N-dimethylethylenediamine and N,N-dimethylformamide in S1 is 2.31-2.35 g:0.82-0.85 g:50-60 mL.

5. The cellulose sulfonate-containing cement according to claim 3, characterized in that The temperature of the heating reaction in S1 is 65-80°C.

6. The cellulose sulfonate-containing cement according to claim 3, characterized in that The mass ratio of toluene diisocyanate, polytetrahydrofuran diol, dibutyltin dilaurate and intermediate 1 in S2 is 0.8-0.9g:1.22-1.26g:0.01-0.02g:0.4-0.5g.

7. The cellulose sulfonate-containing cement according to claim 3, characterized in that The usage ratio of N,N-dimethylformamide, tertiary amino polyurethane and acryl-1,3-sulfonate in S3 is 45-55 mL: 1.13-1.34 g: 4.5-4.7 g.

8. A method for preparing cement containing cellulose sulfonate according to any one of claims 1 to 7, characterized in that: The preparation method of the cement containing cellulose sulfonate is as follows: gypsum, coal gangue and silicate cement clinker are crushed and ball-milled to a particle size of 50-80 μm, and then added into a concrete mixer and stirred for 5-10 minutes, and then cellulose sulfonate, diatomaceous earth, calcium formate and quaternary ammonium salt modified polyurethane are added into the mixer and stirred for 10-15 minutes to obtain the cement containing cellulose sulfonate.

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