A cement containing cellulose sulfonic acid and a preparation method thereof

Abstract

The present invention relates to the technical field of building materials, and discloses a cement containing sulfonic acid cellulose and a preparation method thereof. In the present invention, gypsum, coal gangue, and Portland cement clinker are crushed and added to a concrete mixer for stirring. Then, sulfonic acid cellulose, diatomaceous earth, calcium formate, and quaternary ammonium salt modified polyurethane are added to the stirrer for stirring to obtain the cement containing sulfonic acid cellulose. The cement containing sulfonic acid cellulose of the present invention has good crack resistance, durability, and good mechanical properties.

Description

Technical Field

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

[0002] As an important building material, cement is widely used in many engineering fields such as buildings, roads, bridges, etc. However, traditional cement has certain limitations in performance, such as crack resistance and durability, which need to be further improved. 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 powder and liquid, the powder includes polymethyl methacrylate, esterified starch, initiator and developer, and the liquid includes methyl methacrylate monomer, accelerator and inhibitor. The cement has good mechanical properties, but its crack resistance needs to be improved. Summary of the invention

[0003] 1. Technical issues to be resolved

[0004] In view of the deficiencies of the prior art, the present invention provides a cement containing cellulose sulfonate and a preparation method thereof, which has good crack resistance, durability and good mechanical properties.

[0005] (II) Technical solution

[0006] To achieve the above object, the present invention provides the following technical solution: a cement containing cellulose sulfonate, comprising 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.

[0007] Furthermore, 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 5% sodium hydroxide solution, placed in an ultrasonic pulverizer, ultrasonicated 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, stirred and reacted at 55-60° C. for 6-7 hours, and after completion, the pH of the solution is adjusted to 1-2 with 5% HCl, and then dialyzed and dried to obtain cellulose sulfonate.

[0008] Furthermore, the preparation method of the quaternary ammonium salt modified polyurethane is:

[0009] S1. Add 4-[N,N-bis(2-hydroxyethyl)amino]benzaldehyde and N,N-dimethylethylenediamine into N,N-dimethylformamide solvent, stir and mix them, raise the temperature for reaction for 4 - 6 h, after completion, carry out distillation under reduced pressure, wash, and dry to obtain Intermediate 1;

[0010] S2. Add toluene diisocyanate and polytetrahydrofuran diol into a reaction kettle, then add dibutyltin dilaurate, under a nitrogen atmosphere, carry out prepolymerization, the prepolymerization temperature is 70 - 90 °C, and the time is 2 - 3 h, then add Intermediate 1, stir for chain extension reaction, react at 50 - 60 °C for 20 - 25 min, after the reaction is completed, cool naturally to obtain tertiary amino polyurethane;

[0011] S3. Add tertiary amino polyurethane and allyl-1,3-sultone into N,N-dimethylformamide solvent, 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, carry out rotary evaporation and filtration to obtain quaternary ammonium salt modified polyurethane.

[0012] Further, 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.

[0013] Further, in S1, the reaction temperature is 65 - 80 °C.

[0014] Further, 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.

[0015] Further, 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.

[0016] Further, the preparation method of the cement containing sulfonic acid cellulose is as follows: Crush gypsum, coal gangue, and Portland cement clinker, ball mill them to a particle size of 50 - 80 μm, add them into a concrete mixer, stir for 5 - 10 min, 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.

[0017] (III) Beneficial technical effects

[0018] The present invention involves pulverizing gypsum, coal gangue, and Portland cement clinker, adding them to a concrete mixer, stirring, and then adding sulfonic acid cellulose, diatomaceous earth, calcium formate, and quaternary ammonium salt-modified polyurethane to the stirrer and stirring to obtain cement containing sulfonic acid cellulose.

[0019] The sodium sulfonate groups in the 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 the concrete, the water consumption can be reduced, improving the strength and durability of the cement, and jointly achieving a good water-reducing effect. The polyurethane and quaternary ammonium salt in the quaternary ammonium salt-modified polyurethane can improve the mechanical properties and crack resistance of the cement. The cellulose in the sulfonic acid cellulose-containing cement can form a three-dimensional spatial network structure in the cement. It interweaves with other components in the cement and fills the pores in the cement, enhancing the toughness and crack resistance of the cement. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 It is the reaction equation of Intermediate 1.

[0021] Figure 2 It is the NMR spectrum of Intermediate 1. DETAILED DESCRIPTION OF THE INVENTION

[0022] 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. 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 fall within the scope of protection of the present invention.

[0023] 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.

[0024] Example 1

[0025] 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;

[0026] 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 carry out prepolymerization under a nitrogen atmosphere. The prepolymerization temperature is 70 °C and the time is 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;

[0027] S3. Add 1.13 g of tertiary amino polyurethane and 4.5 g of allyl-1,3-sultone to 45 mL of N,N-dimethylformamide solvent, then continue to add a sodium hydroxide solution with a mass fraction of 3%. React at 50 °C for 4 h. After completion, perform rotary evaporation and filtration to obtain quaternary ammonium salt modified polyurethane;

[0028] S4. Add 1.9 g of nanocrystalline cellulose to 90 mL of a sodium hydroxide solution with a mass fraction of 5%, place it in an ultrasonic disintegrator, ultrasonicate for 15 min, then stir at 45 °C for 2 h. Continue to add 2.3 g of 1,4-butane sultone 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;

[0029] 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 mixer and stir for 10 min to obtain cement containing sulfonated cellulose.

[0030] Example 2

[0031] 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, perform vacuum distillation, wash, and dry to obtain intermediate 1;

[0032] 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. The prepolymerization temperature is 90 °C and the time is 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 polyurethane;

[0033] S3. Add 1.34 g of tertiary amine-based polyurethane and 4.7 g of allyl-1,3-sultone to 55 mL of N,N-dimethylformamide solvent, and then continue to add a 6% sodium hydroxide solution thereto. React at 55 °C for 7 h. After completion, perform rotary evaporation and filtration to obtain quaternary ammonium salt-modified polyurethane;

[0034] S4. Add 2.1 g of nanocrystalline cellulose to 100 mL of a 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 perform dialysis and drying to obtain sulfonated cellulose;

[0035] 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 to a particle size of 80 μm, add to a concrete mixer, stir for 10 min, and then add 2 parts by weight of sulfonated 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 mixer and stir for 15 min to obtain cement containing sulfonated cellulose.

[0036] Example 3

[0037] 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;

[0038] S2. Add 0.85 g of toluene diisocyanate and 1.24 g of polytetrahydrofuran diol to a reaction kettle, and then add 0.015 g of dibutyltin dilaurate. Under a nitrogen atmosphere, perform prepolymerization at a temperature of 80 °C for 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 amine-based polyurethane;

[0039] S3. Add 1.25 g of tertiary amine-based polyurethane and 4.6 g of allyl-1,3-sultone to 50 mL of N,N-dimethylformamide solvent, and then continue to add a 4% sodium hydroxide solution thereto. React at 52 °C for 5 h. After completion, perform rotary evaporation and filtration to obtain quaternary ammonium salt-modified polyurethane;

[0040] S4. Add 2.0 g of nanocrystalline cellulose to 95 mL of a 5% sodium hydroxide solution, place it in an ultrasonic disintegrator, ultrasonicate for 17 min, then stir at 48 °C for 3 h. Then 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 sulfonated cellulose;

[0041] 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.

[0042] Example 4

[0043] 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;

[0044] 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 carry out prepolymerization under a nitrogen atmosphere at a prepolymerization 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;

[0045] 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, react at 55 °C for 7 h. After completion, carry out rotary evaporation and filtration to obtain quaternary ammonium salt modified polyurethane;

[0046] S4. Add 2.0 g of nanocrystalline cellulose to 95 mL of a 5% sodium hydroxide solution, place it in an ultrasonic disintegrator, ultrasonicate for 17 min, then stir at 48 °C for 3 h. Then 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 sulfonated cellulose;

[0047] S5. Grind 13 parts by weight of gypsum, 12 parts by weight of coal gangue, and 65 parts by weight of Portland cement clinker to a particle size of 70 μm by ball milling, 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 diatomaceous earth, 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.

[0048] Comparative Example 1

[0049] Compared with Example 4, the difference in this comparative example is that tertiary amine group polyurethane is used instead of quaternary ammonium salt modified polyurethane.

[0050] Comparative Example 2

[0051] Compared with Example 4, the difference in this comparative example is that quaternary ammonium salt modified polyurethane is not added.

[0052] Comparative Example 3

[0053] Compared with Example 4, the difference in this comparative example is that sulfonic acid cellulose is not added.

[0054] The flexural strength and compressive strength are tested according to the GB / T17671 standard, and the test results are shown in Table 1.

[0055] Table 1: Mechanical property test.

[0056]

[0057] 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.

[0058] The test method for the dry shrinkage rate at 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%.

[0059] Table 2: Shrinkage rate test.

[0060]

[0061] 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.

[0062] It should be noted that in this text, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, such that a process, method, article or device comprising a series of elements not only includes those elements but also other elements not explicitly listed, or further includes elements inherent to such process, method, article or device. Without further limitation, an element defined by the statement "comprising one..." does not exclude the presence of additional identical elements in the process, method, article or device comprising said element.

[0063] The above embodiments are only used to illustrate the technical solutions of the present invention and are not intended 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 described in the foregoing embodiments or perform equivalent replacements for some of the technical features; and these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

[0064] 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 sulfonic acid, characterized in that, It includes the following weight components: 1-2 parts by weight of cellulose sulfonate, 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; The preparation method of the cellulose sulfonate is as follows: Add 1.9-2.1 g of nanocrystalline cellulose into 90-100 mL of sodium hydroxide solution with a mass fraction of 5%, put it into an ultrasonic crusher, ultrasonicate for 15-18 min, then stir at 45-50 °C for 2-4 h. Continuously add 2.3-3.1 g of 1,4-butanesultone, stir and react at 55-60 °C for 6-7 h. After the reaction, adjust the pH of the solution to 1-2 with 5% HCl, then dialyze and dry to obtain cellulose sulfonate; 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 into N,N-dimethylformamide solvent, stir and mix, heat up and react for 4-6 h. After the reaction, carry out vacuum distillation, wash and dry 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 for 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, then continue to add sodium hydroxide solution with a mass fraction of 3-6%, react at 50-55 °C for 4-7 h. After the reaction ends, carry out rotary evaporation and filtration to obtain quaternary ammonium salt modified polyurethane; In the 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; In the S1, the temperature for the heating reaction is 65-80 °C; In the 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; In the 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.

2. A method for preparing a cement containing cellulose sulfonic acid as described in claim 1, characterized in that, The preparation method of the cement containing cellulose sulfonate is as follows: Crush gypsum, coal gangue, and Portland cement clinker, ball mill to a particle size of 50-80 μm, add it into a concrete mixer, stir for 5-10 min, then add cellulose sulfonate, diatomite, calcium formate, and quaternary ammonium salt modified polyurethane into the stirrer, stir for 10-15 min to obtain the cement containing cellulose sulfonate.

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