High-durability cement-based composite material and preparation method thereof

Abstract

The invention relates to the technical field of ocean engineering, and discloses a high-durability cement-based composite material and a preparation method thereof. The high-durability cement-based composite material is prepared from the following raw materials in parts by mass: 40 to 60 parts of Portland cement, 20 to 30 parts of mixed modified filler, 5 to 10 parts of anti-seepage and corrosion-resistant additive, 3 to 5 parts of retarding and water reducing agent and 60 to 80 parts of water. The compressive strength of the high-durability cement-based composite material can reach 134 MPa, the compressive strength retention rate can reach 96%, and the high-durability cement-based composite material has good mechanical properties and corrosion resistance and can be applied to ocean engineering.

Description

Technical Field

[0001] The present invention relates to the technical field of ocean engineering, and more specifically, to a high-durability cement-based composite material and a preparation method thereof. Background Art

[0002] The marine environment is characterized by high salinity, humidity, and rich in various erosive ions. Structures such as port terminals and cross-sea bridges, when exposed to such an environment for a long time, will suffer serious corrosion damage. However, the corrosion resistance of traditional cement-based composite materials in the marine environment is limited. Therefore, in order to improve the durability of marine engineering structures, extend their service life, and reduce maintenance costs, the development of cement-based composite materials with excellent corrosion resistance has become a research hotspot and urgent need in the field of ocean engineering. Summary of the Invention

[0003] The purpose of the present invention is to provide a high-durability cement-based composite material and a preparation method thereof.

[0004] To achieve the above purpose, the present invention provides the following technical solutions:

[0005] One of the technical solutions of the present invention:

[0006] A high-durability cement-based composite material, comprising the following raw materials in parts by mass:

[0007] 40-60 parts of portland cement, 20-30 parts of mixed modified filler, 5-10 parts of anti-seepage and corrosion-resistant additive, 3-5 parts of retarding water reducer, and 60-80 parts of water.

[0008] Further, the preparation method of the mixed modified filler comprises the following steps:

[0009] 1) Calcine quartz powder to obtain calcined modified quartz powder;

[0010] 2) Mix the calcined modified quartz powder obtained in step 1) with nano-silica to obtain a premix;

[0011] 3) Place the premix prepared in step 2) in a silane coupling agent for modification to obtain the mixed modified filler.

[0012] Even further, in step 1), the temperature of the calcination treatment is 300-340 °C, and the duration is 1-3 h.

[0013] Even further, in step 2), the mass ratio of the calcined modified quartz powder to nano-silica is (1-3):1.

[0014] Even further, in step 3), the mass-volume ratio of the premix to the silane coupling agent is 1 g:5 mL.

[0015] Further, in step 3), the modification specifically is: standing for modification at room temperature for 12 h.

[0016] Further, the structural formula of the anti-seepage and corrosion-resistant additive is

[0017] In the formula, R = -H, -CH3, -CH2CH3, -CH(CH3)2, -CH(CH3)(CH2CH3) or -CH(CH2CH3)2.

[0018] Further, the preparation method of the anti-seepage and corrosion-resistant additive includes the following steps:

[0019] 1) Placing compound A and compound B in an organic solvent, and adding a catalytic amount of dimethylsulfonium bromide, and reacting to obtain compound C;

[0020] Among them, the structural formula of compound A is:

[0021] Among them, the structural formula of compound B is:

[0022] Among them, the structural formula of compound C is:

[0023] 2) Placing compound C and sodium sulfide in an organic solvent, and reacting to obtain compound D;

[0024] Among them, the structural formula of compound D is:

[0025] 3) Placing compound D and compound E in an organic solvent, and adding a catalytic amount of dimethylsulfonium bromide, and reacting to obtain compound F, namely the anti-seepage and corrosion-resistant additive;

[0026] Among them, the structural formula of compound E is: RCHO;

[0027] Among them, the structural formula of compound F is:

[0028] Further, in step 1), the organic solvent is one or more of acetone, acetonitrile, dimethyl sulfoxide and dimethylformamide.

[0029] Further, in step 1), the molar ratio of compound A to compound B is 1:1.

[0030] Further, in step 1), the reaction specifically is: reacting at 140 - 160 °C for 4 - 6 h.

[0031] Further, in step 2), the organic solvent is one or more of acetone, acetonitrile, dimethyl sulfoxide, and dimethylformamide.

[0032] Further, in step 2), the molar ratio of compound C to sodium sulfide is 1∶(2 - 4).

[0033] Further, in step 2), the reaction specifically is: reacting at 50 - 70 °C for 1 - 2 h.

[0034] Further, in step 3), the organic solvent is one or more of acetone, acetonitrile, dimethyl sulfoxide, and dimethylformamide.

[0035] Further, in step 3), the molar ratio of compound D to compound E is 1∶1.

[0036] Further, in step 3), the reaction specifically is: reacting at 80 - 90 °C for 2 - 4 h.

[0037] The preparation equation of the anti-seepage and corrosion-resistant additive of the present invention is as follows:

[0038]

[0039] The second technical solution of the present invention:

[0040] The preparation method of the above-mentioned high-durability cement-based composite material includes the following steps:

[0041] Mix silicate cement, mixed modified filler, anti-seepage and corrosion-resistant additive, retarder and water, and stir at room temperature for 30 min to obtain the high-durability cement-based composite material.

[0042] The third technical solution of the present invention:

[0043] The application of the above-mentioned high-durability cement-based composite material as a grouting material in ocean engineering.

[0044] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0045] The high-durability cement-based composite material provided by the present invention has a compressive strength of up to 134 MPa and a compressive strength retention rate of up to 96%, has good mechanical properties and corrosion resistance, and can be applied to ocean engineering. Specific Embodiments

[0046] The various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but should be understood as a more detailed description of certain aspects, characteristics, and implementation schemes of the present invention. It should be understood that the terms described in the present invention are only for describing specific embodiments and are not used to limit the present invention.

[0047] In addition, for the numerical ranges in the present invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Each intermediate value within any stated value or stated range, as well as each smaller range between any other stated value or intermediate value within the stated range, is also included in the present invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0048] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. Although the present invention only describes preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials related to those documents. In case of conflict with any incorporated document, the content of this specification shall prevail.

[0049] Without departing from the scope or spirit of the present invention, various improvements and changes can be made to the specific embodiments of the description of the present invention, which are obvious to those skilled in the art. Other embodiments obtained from the description of the present invention are obvious to those skilled in the art. The description and examples of the present invention are merely exemplary.

[0050] Regarding the use of "comprising", "including", "having", "containing", etc. herein, they are all open-ended terms, meaning including but not limited to.

[0051] In the following examples, all raw materials used are commercially available, and those skilled in the art can arbitrarily select raw materials of different specifications according to the actual situation; to better illustrate the performance of the high-durability cement-based composite material of the present invention, in the following examples, the portland cement is portland cement 52.5R, the retarder and water reducer is naphthalene sulfonate formaldehyde condensate, the quartz powder is 600-mesh quartz powder, the nano-silica is 1300-mesh nano-silica, and the silane coupling agent is silane coupling agent kh560.

[0052] In the following examples, a preparation method of a high-durability cement-based composite material includes the following steps:

[0053] 1. Preparation of mixed modified filler

[0054] 1) Under a nitrogen atmosphere, the quartz powder is calcined to obtain calcined modified quartz powder;

[0055] Among them, the temperature of the calcination treatment is 300 - 340 °C, and the duration is 1 - 3 h;

[0056] 2) mixing the calcined modified quartz powder obtained in step 1) with nano-silica in a mass ratio of calcined modified quartz powder to nano-silica of (1-3):1 to obtain a premix;

[0057] 3) placing the premix prepared in step 2) in the silane coupling agent at a mass volume ratio of the premix to the silane coupling agent of 1 g:5 mL, and allowing the mixture to stand at room temperature for 12 hours to undergo modification, thereby obtaining the mixed modified filler;

[0058] 2. Preparation of anti-seepage and corrosion-resistant additives

[0059] 1) Compound A and Compound B are placed in an organic solvent at a molar ratio of 1:1, and a catalytic amount of dimethylsulfonium bromide (BDMS) is added, and the mixture is reacted at 140-160° C. for 4-6 hours to obtain Compound C;

[0060] Wherein, the structural formula of compound A is:

[0061] Wherein, the structural formula of compound B is:

[0062] Wherein, the structural formula of compound C is:

[0063] Wherein, the organic solvent is one or more of acetone, acetonitrile, dimethyl sulfoxide and dimethylformamide;

[0064] 2) Compound C and sodium sulfide are placed in an organic solvent at a molar ratio of 1:(2-4), and reacted at 50-70° C. for 1-2 hours to obtain Compound D;

[0065] Wherein, the structural formula of compound D is:

[0066] Wherein, the organic solvent is one or more of acetone, acetonitrile, dimethyl sulfoxide and dimethylformamide;

[0067] 3) Compound D and Compound E are placed in an organic solvent at a molar ratio of 1:1, and a catalytic amount of dimethylsulfonium bromide is added, and the mixture is reacted at 80-90° C. for 2-4 hours to obtain Compound F, which is the anti-seepage and anti-corrosion additive;

[0068] Among them, the structural formula of compound E is: RCHO;

[0069] Wherein, the structural formula of compound F is:

[0070] Wherein, R=-H, -CH3, -CH2CH3, -CH(CH3)2, -CH(CH3)(CH2CH3) or -CH(CH2CH3)2;

[0071] Wherein, the organic solvent is one or more of acetone, acetonitrile, dimethyl sulfoxide and dimethylformamide;

[0072] 3. Preparation of high-durability cement-based composite materials

[0073] 1) Weigh each raw material according to the following parts by mass:

[0074] 40-60 parts of Portland cement, 20-30 parts of mixed modified filler, 5-10 parts of anti-seepage and corrosion-resistant additive, 3-5 parts of retarding water-reducing agent, and 60-80 parts of water;

[0075] 2) The raw materials weighed in step 1) are mixed and stirred at room temperature for 30 minutes to obtain the high-durability cement-based composite material.

[0076] Example 1

[0077] A highly durable cement-based composite material

[0078] 1. Preparation of mixed modified fillers

[0079] 1) calcining the quartz powder in a nitrogen atmosphere to obtain calcined modified quartz powder;

[0080] The calcination temperature is 300°C and the duration is 1 hour.

[0081] 2) mixing the calcined modified quartz powder obtained in step 1) with nano-silica in a mass ratio of 1:1 to obtain a premix;

[0082] 3) placing the premix prepared in step 2) in the silane coupling agent at a mass volume ratio of the premix to the silane coupling agent of 1 g:5 mL, and allowing the mixture to stand at room temperature for 12 hours to undergo modification, thereby obtaining the mixed modified filler;

[0083] 2. Preparation of anti-seepage and corrosion-resistant additives

[0084] In this embodiment, the anti-seepage and corrosion-resistant additive is prepared according to the following preparation formula:

[0085]

[0086] 1) Compound A and Compound B were placed in dimethylformamide at a molar ratio of 1:1, and a catalytic amount of BDMS was added, and the mixture was reacted at 150° C. for 5 h to obtain Compound C;

[0087] 2) Place compound C and sodium sulfide in dimethylformamide according to the molar ratio of compound C to sodium sulfide of 1:2, and react at 60 °C for 2 h to obtain compound D;

[0088] 3) Place compound D and compound E in dimethylformamide according to the molar ratio of compound D to compound E of 1:1, add a catalytic amount of dimethylsulfonium bromide, and react at 80 °C for 2 h to obtain compound F, namely the anti-seepage and corrosion-resistant additive;

[0089] 3. Preparation of high-durability cement-based composite material

[0090] 1) Weigh each raw material according to the following parts by mass:

[0091] 40 parts of portland cement, 20 parts of mixed modified filler, 5 parts of anti-seepage and corrosion-resistant additive, 3 parts of retarder and water reducer, and 60 parts of water;

[0092] 2) Mix the raw materials weighed in step 1) and stir at room temperature for 30 min to obtain the high-durability cement-based composite material.

[0093] Example 2

[0094] A high-durability cement-based composite material

[0095] 1. Preparation of mixed modified filler

[0096] 1) Calcinate quartz powder under a nitrogen atmosphere to obtain calcined modified quartz powder;

[0097] Among them, the temperature of the calcination treatment is 320 °C and the duration is 2 h;

[0098] 2) Mix the calcined modified quartz powder obtained in step 1) and nano-silica according to the mass ratio of calcined modified quartz powder to nano-silica of 2:1 to obtain a premix;

[0099] 3) Place the premix prepared in step 2) in a silane coupling agent according to the mass-volume ratio of premix to silane coupling agent of 1 g:5 mL, and let it stand for modification at room temperature for 12 h to obtain the mixed modified filler;

[0100] 2. Preparation of anti-seepage and corrosion-resistant additive

[0101] This example prepares the anti-seepage and corrosion-resistant additive with reference to the following preparation equation:

[0102]

[0103] 1) Place compound A and compound B in dimethylformamide according to a molar ratio of 1:1, add a catalytic amount of BDMS, and react at 150 °C for 5 h to obtain compound C;

[0104] 2) Place compound C and sodium sulfide in dimethylformamide according to a molar ratio of 1:2, and react at 60 °C for 2 h to obtain compound D;

[0105] 3) Place compound D and compound E in dimethylformamide according to a molar ratio of 1:1, add a catalytic amount of dimethylsulfonium bromide, and react at 80 °C for 2 h to obtain compound F, namely the anti-seepage and corrosion-resistant additive;

[0106] 3. Preparation of high-durability cement-based composite

[0107] 1) Weigh each raw material according to the following parts by mass:

[0108] Portland cement 50 parts, mixed modified filler 25 parts, anti-seepage and corrosion-resistant additive 6 parts, retarding water reducer 4 parts, water 70 parts;

[0109] 2) Mix the raw materials weighed in step 1) and stir at room temperature for 30 min to obtain the high-durability cement-based composite.

[0110] Example 3

[0111] A high-durability cement-based composite

[0112] 1. Preparation of mixed modified filler

[0113] 1) In a nitrogen atmosphere, calcine quartz powder to obtain calcined modified quartz powder;

[0114] Among them, the temperature of the calcination treatment is 340 °C and the duration is 3 h;

[0115] 2) Mix the calcined modified quartz powder obtained in step 1) and nano-silica according to a mass ratio of 3:1 to obtain a premix;

[0116] 3) Place the premix prepared in step 2) in a silane coupling agent according to a mass-volume ratio of 1 g:5 mL, and let it stand for modification at room temperature for 12 h to obtain the mixed modified filler;

[0117] 2. Preparation of anti-seepage and corrosion-resistant additive

[0118] This example prepares the anti-seepage and corrosion-resistant additive with reference to the following preparation equation:

[0119]

[0120] 1) Place compound A and compound B in dimethylformamide according to the molar ratio of compound A to compound B of 1:1, add a catalytic amount of BDMS, and react at 150 °C for 5 h to obtain compound C;

[0121] 2) Place compound C and sodium sulfide in dimethylformamide according to the molar ratio of compound C to sodium sulfide of 1:2, and react at 60 °C for 2 h to obtain compound D;

[0122] 3) Place compound D and compound E in dimethylformamide according to the molar ratio of compound D to compound E of 1:1, add a catalytic amount of dimethylsulfonium bromide, and react at 80 °C for 2 h to obtain compound F, i.e., the anti-seepage and corrosion-resistant additive;

[0123] 3. Preparation of high-durability cement-based composite

[0124] 1) Weigh each raw material according to the following parts by mass:

[0125] 60 parts of portland cement, 30 parts of mixed modified filler, 10 parts of anti-seepage and corrosion-resistant additive, 5 parts of retarding water reducer, 80 parts of water;

[0126] 2) Mix the raw materials weighed in step 1) and stir at room temperature for 30 min to obtain the high-durability cement-based composite.

[0127] Example 4

[0128] A high-durability cement-based composite

[0129] 1. Preparation of mixed modified filler

[0130] 1) Calcinate quartz powder under a nitrogen atmosphere to obtain calcined modified quartz powder;

[0131] Among them, the temperature of the calcination treatment is 320 °C and the duration is 2 h;

[0132] 2) Mix the calcined modified quartz powder obtained in step 1) and nano-silica according to the mass ratio of calcined modified quartz powder to nano-silica of 2:1 to obtain a premix;

[0133] 3) Place the premix prepared in step 2) in a silane coupling agent according to the mass-volume ratio of premix to silane coupling agent of 1 g:5 mL, and let it stand for modification at room temperature for 12 h to obtain the mixed modified filler;

[0134] 2. Preparation of anti-seepage and corrosion-resistant additive

[0135] In this embodiment, the anti-seepage and corrosion-resistant additive is prepared with reference to the following preparation equation:

[0136]

[0137] 1) According to the molar ratio of compound A to compound B being 1:1, compound A and compound B are placed in dimethylformamide, and a catalytic amount of BDMS is added, and the reaction is carried out at 150 °C for 5 h to obtain compound C;

[0138] 2) According to the molar ratio of compound C to sodium sulfide being 1:2, compound C and sodium sulfide are placed in dimethylformamide, and the reaction is carried out at 60 °C for 2 h to obtain compound D;

[0139] 3) According to the molar ratio of compound D to compound E being 1:1, compound D and compound E are placed in dimethylformamide, and a catalytic amount of dimethylsulfonium dibromide is added, and the reaction is carried out at 83 °C for 3 h to obtain compound F, that is, the anti-seepage and corrosion-resistant additive;

[0140] 3. Preparation of high-durability cement-based composite

[0141] 1) Weigh each raw material according to the following parts by mass:

[0142] 50 parts of portland cement, 25 parts of mixed modified filler, 6 parts of anti-seepage and corrosion-resistant additive, 4 parts of retarder and water reducer, 70 parts of water;

[0143] 2) Mix the raw materials weighed in step 1) and stir at room temperature for 30 min to obtain the high-durability cement-based composite.

[0144] Example 5

[0145] A high-durability cement-based composite

[0146] 1. Preparation of mixed modified filler

[0147] 1) In a nitrogen atmosphere, the quartz powder is calcined to obtain calcined modified quartz powder;

[0148] Among them, the temperature of the calcination treatment is 320 °C and the duration is 2 h;

[0149] 2) According to the mass ratio of the calcined modified quartz powder to nano-silica being 2:1, the calcined modified quartz powder obtained in step 1) and nano-silica are mixed to obtain a premix;

[0150] 3) According to the mass-volume ratio of the premix to the silane coupling agent being 1 g:5 mL, the premix prepared in step 2) is placed in the silane coupling agent and left to stand for modification at room temperature for 12 h to obtain the mixed modified filler;

[0151] 2. Preparation of Anti-seepage and Corrosion-resistant Additive

[0152] In this example, the anti-seepage and corrosion-resistant additive is prepared with reference to the following preparation equation:

[0153]

[0154] 1) According to the molar ratio of compound A to compound B being 1:1, compound A and compound B are placed in dimethylformamide, and a catalytic amount of BDMS is added, and the reaction is carried out at 150 °C for 5 h to obtain compound C;

[0155] 2) According to the molar ratio of compound C to sodium sulfide being 1:2, compound C and sodium sulfide are placed in dimethylformamide, and the reaction is carried out at 60 °C for 2 h to obtain compound D;

[0156] 3) According to the molar ratio of compound D to compound E being 1:1, compound D and compound E are placed in dimethylformamide, and a catalytic amount of dimethylsulfonium bromide is added, and the reaction is carried out at 85 °C for 4 h to obtain compound F, that is, the anti-seepage and corrosion-resistant additive;

[0157] 3. Preparation of High-durability Cement-based Composite Material

[0158] 1) Weigh each raw material according to the following parts by mass:

[0159] Portland cement 50 parts, mixed modified filler 25 parts, anti-seepage and corrosion-resistant additive 6 parts, retarder and water reducer 4 parts, water 70 parts;

[0160] 2) Mix the raw materials weighed in step 1) and stir at room temperature for 30 min to obtain the high-durability cement-based composite material.

[0161] Example 6

[0162] A high-durability cement-based composite material

[0163] 1. Preparation of Mixed Modified Filler

[0164] 1) In a nitrogen atmosphere, the quartz powder is calcined to obtain calcined modified quartz powder;

[0165] Among them, the temperature of the calcination treatment is 320 °C and the duration is 2 h;

[0166] 2) According to the mass ratio of calcined modified quartz powder to nano-silica being 2:1, the calcined modified quartz powder obtained in step 1) and nano-silica are mixed to obtain a premix;

[0167] 3) According to the mass-volume ratio of the premix to the silane coupling agent being 1 g∶5 mL, place the premix prepared in step 2) into the silane coupling agent, and let it stand for modification at room temperature for 12 h to obtain the mixed modified filler;

[0168] 2. Preparation of the anti-seepage and corrosion-resistant additive

[0169] In this example, the anti-seepage and corrosion-resistant additive is prepared with reference to the following preparation equation:

[0170]

[0171] 1) According to the molar ratio of compound A to compound B being 1∶1, place compound A and compound B in dimethylformamide, and add a catalytic amount of BDMS, and react at 150 °C for 5 h to obtain compound C;

[0172] 2) According to the molar ratio of compound C to sodium sulfide being 1∶2, place compound C and sodium sulfide in dimethylformamide, and react at 60 °C for 2 h to obtain compound D;

[0173] 3) According to the molar ratio of compound D to compound E being 1∶1, place compound D and compound E in dimethylformamide, and add a catalytic amount of dimethylsulfonium bromide, and react at 90 °C for 3 h to obtain compound F, which is the anti-seepage and corrosion-resistant additive;

[0174] 3. Preparation of the high-durability cement-based composite material

[0175] 1) Weigh each raw material according to the following mass parts:

[0176] Portland cement 50 parts, mixed modified filler 25 parts, anti-seepage and corrosion-resistant additive 6 parts, retarder and water reducer 4 parts, water 70 parts;

[0177] 2) Mix the raw materials weighed in step 1), and stir at room temperature for 30 min to obtain the high-durability cement-based composite material.

[0178] Example 7

[0179] A high-durability cement-based composite material

[0180] 1. Preparation of the mixed modified filler

[0181] 1) Under a nitrogen atmosphere, conduct calcination treatment on the quartz powder to obtain calcined modified quartz powder;

[0182] Among them, the temperature of the calcination treatment is 320 °C, and the duration is 2 h;

[0183] 2) Mix the calcined modified quartz powder obtained in step 1) and nano-silica according to the mass ratio of the calcined modified quartz powder to nano-silica of 2:1 to obtain a premix;

[0184] 3) Place the premix prepared in step 2) in a silane coupling agent according to the mass-volume ratio of the premix to the silane coupling agent of 1 g:5 mL, and let it stand for modification at room temperature for 12 h to obtain the mixed modified filler;

[0185] 2. Preparation of the anti-seepage and corrosion-resistant additive

[0186] In this example, the anti-seepage and corrosion-resistant additive is prepared with reference to the following preparation equation:

[0187]

[0188] 1) Place compound A and compound B in dimethylformamide according to the molar ratio of compound A to compound B of 1:1, add a catalytic amount of BDMS, and react at 150 °C for 5 h to obtain compound C;

[0189] 2) Place compound C and sodium sulfide in dimethylformamide according to the molar ratio of compound C to sodium sulfide of 1:2, and react at 60 °C for 2 h to obtain compound D;

[0190] 3) Place compound D and compound E in dimethylformamide according to the molar ratio of compound D to compound E of 1:1, add a catalytic amount of dimethylsulfonium bromide, and react at 90 °C for 4 h to obtain compound F, that is, the anti-seepage and corrosion-resistant additive;

[0191] 3. Preparation of the high-durability cement-based composite material

[0192] 1) Weigh each raw material according to the following parts by mass:

[0193] Portland cement 50 parts, mixed modified filler 25 parts, anti-seepage and corrosion-resistant additive 6 parts, retarder and water reducer 4 parts, water 70 parts;

[0194] 2) Mix the raw materials weighed in step 1) and stir at room temperature for 30 min to obtain the high-durability cement-based composite material.

[0195] Example 8

[0196] A high-durability cement-based composite material

[0197] 1. Preparation of the mixed modified filler

[0198] 1) Under a nitrogen atmosphere, perform a calcination treatment on the quartz powder to obtain a calcined modified quartz powder;

[0199] Among them, the temperature of the calcination treatment is 320 °C and the duration is 2 h;

[0200] 2) Mix the calcined modified quartz powder obtained in step 1) and nano-silica according to the mass ratio of the calcined modified quartz powder to nano-silica of 2:1 to obtain a premix;

[0201] 3) Place the premix prepared in step 2) in a silane coupling agent according to the mass-volume ratio of the premix to the silane coupling agent of 1 g:5 mL, and let it stand for modification at room temperature for 12 h to obtain the mixed modified filler;

[0202] 2. Preparation of the anti-seepage and corrosion-resistant additive

[0203] In this example, the anti-seepage and corrosion-resistant additive is prepared with reference to the following preparation equation:

[0204]

[0205] 1) Place compound A and compound B in dimethylformamide according to the molar ratio of compound A to compound B of 1:1, add a catalytic amount of BDMS, and react at 150 °C for 5 h to obtain compound C;

[0206] 2) Place compound C and sodium sulfide in dimethylformamide according to the molar ratio of compound C to sodium sulfide of 1:2, and react at 60 °C for 2 h to obtain compound D;

[0207] 3) Place compound D and compound E in dimethylformamide according to the molar ratio of compound D to compound E of 1:1, add a catalytic amount of dimethylsulfonium bromide, and react at 90 °C for 4 h to obtain compound F, that is, the anti-seepage and corrosion-resistant additive;

[0208] 3. Preparation of the high-durability cement-based composite material

[0209] 1) Weigh each raw material according to the following parts by mass:

[0210] 50 parts of portland cement, 25 parts of mixed modified filler, 6 parts of anti-seepage and corrosion-resistant additive, 4 parts of retarder and water-reducing agent, 70 parts of water;

[0211] 2) Mix the raw materials weighed in step 1) and stir at room temperature for 30 min to obtain the high-durability cement-based composite material.

[0212] Comparative Example 1

[0213] A cement-based composite material

[0214] Same as Example 6, the difference is only that the preparation of the mixed modified filler in step 1 is as follows:

[0215] 1) Mix quartz powder and nano-silica according to a mass ratio of 2:1 to obtain a premix.

[0216] 2) Place the premix prepared in step 1) in a silane coupling agent according to a mass-volume ratio of 1 g:5 mL, and let it stand for modification at room temperature for 12 h to obtain the mixed modified filler.

[0217] Comparative Example 2

[0218] A cement-based composite material

[0219] Same as Example 6, except that the preparation of the mixed modified filler in step 1 is as follows:

[0220] 1) Calcinate quartz powder in a nitrogen atmosphere to obtain calcined modified quartz powder.

[0221] Among them, the temperature of the calcination treatment is 320 °C and the duration is 2 h.

[0222] 2) Place the calcined modified quartz powder obtained in step 1) in a silane coupling agent according to a mass-volume ratio of 1 g:5 mL, and let it stand for modification at room temperature for 12 h to obtain the mixed modified filler.

[0223] Comparative Example 3

[0224] A cement-based composite material

[0225] Same as Example 6, except that the preparation of the mixed modified filler in step 1 is as follows:

[0226] 1) Calcinate quartz powder in a nitrogen atmosphere to obtain calcined modified quartz powder.

[0227] Among them, the temperature of the calcination treatment is 320 °C and the duration is 2 h.

[0228] 2) Mix the calcined modified quartz powder obtained in step 1) and nano-silica according to a mass ratio of 2:1 to obtain the mixed modified filler.

[0229] Comparative Example 4

[0230] A cement-based composite material

[0231] Same as Example 6, except that the preparation of the anti-seepage and corrosion-resistant additive is omitted, and the preparation of the high-durability cement-based composite material in step 3 is as follows:

[0232] 1) Weigh each raw material according to the following parts by mass:

[0233] 50 parts of portland cement, 25 parts of mixed modified filler, 4 parts of retarder water reducer, 70 parts of water;

[0234] 2) Mix the raw materials weighed in step 1) and stir at room temperature for 30 min to obtain a cement-based composite material.

[0235] Effect verification

[0236] Perform compressive strength testing (ASTM D695-15) and salt spray tolerance testing (ASTM B117) on the high-durability cement-based composite materials prepared in Examples 1 to 8 and the cement-based composite materials prepared in Comparative Examples 1 to 4; the test results of compressive strength and salt spray tolerance are shown in Table 1;

[0237] Table 1 Test results of compressive strength and salt spray tolerance

[0238]

[0239]

[0240] It can be seen from the data in Table 1 that a high-durability cement-based composite material provided by the present invention has a compressive strength of up to 134 MPa and a compressive strength retention rate of up to 96%, has good mechanical properties and corrosion resistance, and can be applied to ocean engineering.

[0241] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit them. Although the present invention has been described in detail with reference to the above embodiments, those of ordinary skill in the art should understand that: modifications or equivalent replacements can still be made to the specific embodiments of the present invention. Any modification or equivalent replacement that does not depart from the spirit and scope of the present invention shall be covered by the protection scope of the claims of the present invention.

Claims

1. A highly durable cement-based composite material, characterized in that, It comprises the following raw materials in parts by mass: 40 - 60 parts of portland cement, 20 - 30 parts of mixed modified filler, 5 - 10 parts of anti-seepage and corrosion-resistant additive, 3 - 5 parts of retarder water reducer, and 60 - 80 parts of water.

2. The high-durability cement-based composite material according to claim 1, characterized in that, The preparation method of the mixed modified filler comprises the following steps: 1) Calcine quartz powder to obtain calcined modified quartz powder; 2) Mix the calcined modified quartz powder obtained in step 1) with nano-silica to obtain a premix; 3) Place the premix prepared in step 2) in a silane coupling agent for modification to obtain the mixed modified filler.

3. A high-durability cement-based composite material according to claim 2, wherein in step 1), the temperature of the calcination treatment is 300 - 340 °C, and the duration is 1 - 3 h; in step 2), the mass ratio of the calcined modified quartz powder to nano-silica is (1 - 3)∶1; in step 3), the mass-volume ratio of the premix to the silane coupling agent is 1 g∶5 mL; the modification specifically is: standing for modification at room temperature for 12 h.

4. A highly durable cement-based composite material according to claim 1, characterized in that The structural formula of the anti-seepage and corrosion-resistant additive is In the formula, R = -H, -CH3, -CH2CH3, -CH(CH3)2, -CH(CH3)(CH2CH3) or -CH(CH2CH3)2.

5. A highly durable cement-based composite material according to claim 4, characterized in that, The preparation method of the anti-seepage and corrosion-resistant additive comprises the following steps: 1) Place compound A and compound B in an organic solvent, and add a catalytic amount of dimethylsulfonium bromide, and react to obtain compound C; Among them, the structural formula of Compound A is: Among them, the structural formula of compound B is: Among them, the structural formula of compound C is: 2) Place compound C and sodium sulfide in an organic solvent, and react to obtain compound D; Among them, the structural formula of compound D is: 3) Place compound D and compound E in an organic solvent, and add a catalytic amount of dimethylsulfonium bromide, and react to obtain compound F, namely the anti-seepage and corrosion-resistant additive; wherein, the structural formula of compound E is: RCHO; Among them, the structural formula of compound F is:

6. A high-durability cement-based composite material according to claim 5, wherein in step 1), the molar ratio of compound A to compound B is 1∶1; the reaction specifically is: reacting at 140 - 160 °C for 4 - 6 h; in step 2), the molar ratio of compound C to sodium sulfide is 1∶(2 - 4); the reaction specifically is: reacting at 50 - 70 °C for 1 - 2 h; in step 3), the molar ratio of compound D to compound E is 1∶1; the reaction specifically is: reacting at 80 - 90 °C for 2 - 4 h.

7. A method for preparing a highly durable cement-based composite material according to any one of claims 1 to 6, characterized in that, It comprises the following steps: Mix portland cement, mixed modified filler, anti-seepage and corrosion-resistant additive, retarder water reducer and water, and stir at room temperature for 30 min to obtain the high-durability cement-based composite material.

8. The application of a high-durability cement-based composite material according to any one of claims 1 - 6 as a grouting material in ocean engineering.

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