A high-performance concrete admixture composition for a wind power tower and a preparation method thereof

Abstract

The application relates to a high-performance concrete admixture composition for a wind power tower drum and a preparation method thereof, relates to the field of concrete admixtures, and comprises the following components in parts by weight: 35-45 parts of a shrinkage-reducing polycarboxylate water reducing agent, 8-12 parts of methoxy polyethylene glycol acrylate modified nano silicon dioxide, 1.5-2.5 parts of sodium dodecyl polyoxyethylene ether sulfonate, 0.8-1.5 parts of coconut diethanolamide, 0.3-0.8 parts of sodium polyacrylate, 0.2-0.6 parts of ammonium tripolyphosphate, 0.05-0.15 parts of a polyether defoaming agent and 40-50 parts of water. The application realizes systematic improvement of the microstructure of concrete, significantly improves the strength and durability of the concrete by synergistically regulating the hydration process of the concrete, optimizing the pore structure in the concrete and strengthening the interface transition zone through the synergistic effect among the various admixtures.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of concrete admixtures, and in particular to a high-performance concrete admixture composition for wind turbine towers and a preparation method thereof. BACKGROUND

[0002] In recent years, the wind power industry has developed rapidly, and wind turbine towers, as key components, have higher requirements for the performance of the concrete used. Not only high strength is required, but also good workability, compactness and corrosion resistance. In order to meet the requirements of high strength, good workability and excellent corrosion resistance, the industry is constantly exploring the research and application of new types of concrete admixtures. These efforts aim to improve the overall performance of concrete, thereby adapting to complex and variable working environments, ensuring the safe and stable operation of wind power facilities, and further promoting the development of clean energy industries.

[0003] Although existing concrete admixtures can improve the performance of concrete to some extent, they often sacrifice workability and durability when increasing strength, thereby affecting the long-term stability of concrete. Therefore, how to effectively coordinate the mutual relationship between various functional components so that concrete has both high strength and high durability has become a key bottleneck that needs to be broken through. SUMMARY

[0004] To solve the above technical problems, the present application provides a high-performance concrete admixture composition for wind turbine towers and a preparation method thereof.

[0005] The present application provides a high-performance concrete admixture composition for wind turbine towers and a preparation method thereof, which adopts the following technical solution:

[0006] A high-performance concrete admixture composition for wind turbine towers, comprising the following components in parts by weight: 35-45 parts of a shrinkage-reducing polycarboxylate superplasticizer, 8-12 parts of methoxy polyethylene glycol acrylate modified nano-silica, 1.5-2.5 parts of sodium dodecyl polyoxyethylene ether sulfonate, 0.8-1.5 parts of cocodihydroxyethylamide, 0.3-0.8 parts of sodium polyacrylate, 0.2-0.6 parts of ammonium tripolyphosphate, 0.05-0.15 parts of polyether defoamer, and 40-50 parts of water.

[0007] By adopting the above technical solution, the present application regulates and optimizes the pore structure inside the concrete and strengthens the interface transition zone through the synergistic effect between various admixtures, thereby realizing the systematic improvement of the microstructure of the concrete and significantly improving the strength and durability of the concrete.

[0008] In one specific embodiment, the high-performance concrete admixture composition for wind power tower includes 42 parts of a shrinkage-reducing polycarboxylate superplasticizer, 10 parts of methoxyl polyethylene glycol acrylate modified nano-silica, 2 parts of sodium dodecyl polyoxyethylene ether sulfonate, 1 part of coconut diethanolamide, 0.6 parts of sodium polyacrylate, 0.4 parts of ammonium tripolyphosphate, 0.1 parts of polyether defoamer, and 43.9 parts of water.

[0009] In one specific comparative example, the high-performance concrete admixture composition for wind power tower includes 42 parts of BL-7 polycarboxylate superplasticizer, 10 parts of methoxyl polyethylene glycol acrylate modified nano-silica, 2 parts of sodium dodecyl polyoxyethylene ether sulfonate, 1 part of coconut diethanolamide, 0.6 parts of sodium polyacrylate, 0.4 parts of ammonium tripolyphosphate, 0.1 parts of polyether defoamer, and 43.9 parts of water.

[0010] In one specific comparative example, the high-performance concrete admixture composition for wind power tower includes 42 parts of BL-7 polycarboxylate superplasticizer, 10 parts of methoxyl polyethylene glycol acrylate modified nano-silica, 2 parts of sodium dodecyl polyoxyethylene ether sulfonate, 1 part of coconut diethanolamide, 0.6 parts of sodium polyacrylate, 0.4 parts of ammonium tripolyphosphate, 0.1 parts of polyether defoamer, and 43.9 parts of water.

[0011] Among them, the high-performance concrete admixture composition for wind power tower prepared by selecting the shrinkage-reducing polycarboxylate superplasticizer provided in the present application has a water absorption rate reduced by 2.34-2.28% compared with the water absorption rate of the high-performance concrete admixture composition for wind power tower prepared by selecting the commercially available BL-7 polycarboxylate superplasticizer and JC-05 polycarboxylate superplasticizer, a 28d compressive strength increased by 24.7-23.9 MPa, an electric flux reduced by 610-570 C, and a freeze-thaw mass loss rate reduced by 2.17-1.78%, indicating that the shrinkage-reducing polycarboxylate superplasticizer provided in the present application has a more excellent effect on improving the strength and durability of concrete compared with other commercially available polycarboxylate superplasticizers.

[0012] In summary, the shrinkage-reducing polycarboxylate superplasticizer can fully play a synergistic effect with other components, and has a significant effect on improving the strength and durability of concrete.

[0013] In one specific embodiment, the high-performance concrete admixture composition for wind power tower includes 35 parts of a shrinkage-reducing polycarboxylate superplasticizer, 12 parts of methoxyl polyethylene glycol acrylate modified nano-silica, 1.5 parts of sodium dodecyl polyoxyethylene ether sulfonate, 1.5 parts of coconut diethanolamide, 0.3 parts of sodium polyacrylate, 0.6 parts of ammonium tripolyphosphate, 0.05 parts of polyether defoamer, and 50 parts of water.

[0014] In one specific embodiment, the high-performance concrete admixture composition for wind turbine towers includes 38 parts of a shrinkage-reducing polycarboxylate superplasticizer, 11 parts of methoxypolyethylene glycol acrylate modified nanosilica, 1.7 parts of sodium dodecyl polyoxyethylene ether sulfonate, 1.2 parts of cocodiethanolamide, 0.4 parts of sodium polyacrylate, 0.5 parts of ammonium tripolyphosphate, 0.08 parts of a polyether defoamer, and 47 parts of water.

[0015] In one specific embodiment, the high-performance concrete admixture composition for wind turbine towers includes 42 parts of a shrinkage-reducing polycarboxylate superplasticizer, 10 parts of methoxypolyethylene glycol acrylate modified nanosilica, 2 parts of sodium dodecyl polyoxyethylene ether sulfonate, 1 part of cocodiethanolamide, 0.6 parts of sodium polyacrylate, 0.4 parts of ammonium tripolyphosphate, 0.1 parts of a polyether defoamer, and 43.9 parts of water.

[0016] In one specific embodiment, the high-performance concrete admixture composition for wind turbine towers includes 45 parts of a shrinkage-reducing polycarboxylate superplasticizer, 8 parts of methoxypolyethylene glycol acrylate modified nanosilica, 2.5 parts of sodium dodecyl polyoxyethylene ether sulfonate, 0.8 parts of cocodiethanolamide, 0.8 parts of sodium polyacrylate, 0.2 parts of ammonium tripolyphosphate, 0.15 parts of a polyether defoamer, and 40 parts of water.

[0017] In one specific embodiment, the high-performance concrete admixture composition for wind turbine towers includes 42 parts of a shrinkage-reducing polycarboxylate superplasticizer, 10 parts of methoxypolyethylene glycol acrylate modified nanosilica, 2 parts of sodium dodecyl polyoxyethylene ether sulfonate, 1 part of cocodiethanolamide, 0.6 parts of sodium polyacrylate, 0.4 parts of ammonium tripolyphosphate, 0.1 parts of a polyether defoamer, and 43.9 parts of water.

[0018] Preferably, the shrinkage-reducing polycarboxylate superplasticizer includes acrylic acid, methylenyl polyoxyethylene ether, and diethylene glycol monobutyl ether maleic anhydride monoester in a molar ratio of (3.5-4.5):(1-1.5):(1.5-2.5).

[0019] By using the above technical solution, the shrinkage-reducing polycarboxylate superplasticizer is prepared by polymerizing acrylic acid, methylenyl polyoxyethylene ether, and diethylene glycol monobutyl ether maleic anhydride monoester, which has both water-reducing effect and shrinkage-reducing performance, can effectively reduce the shrinkage rate of concrete while having the advantages of high water-reducing rate and high slump retention, thereby improving the strength and durability of the concrete.

[0020] In one specific embodiment, the shrinkage-reducing polycarboxylate superplasticizer comprises acrylic acid, methyl allyl polyoxyethylene ether and diethylene glycol monobutyl ether maleic anhydride monoester in a molar ratio of 3.5:1.5:1.5.

[0021] In one specific embodiment, the shrinkage-reducing polycarboxylate superplasticizer comprises acrylic acid, methyl allyl polyoxyethylene ether and diethylene glycol monobutyl ether maleic anhydride monoester in a molar ratio of 3.8:1.1:1.8.

[0022] In one specific embodiment, the shrinkage-reducing polycarboxylate superplasticizer comprises acrylic acid, methyl allyl polyoxyethylene ether and diethylene glycol monobutyl ether maleic anhydride monoester in a molar ratio of 4:1.3:2.

[0023] In one specific embodiment, the shrinkage-reducing polycarboxylate superplasticizer comprises acrylic acid, methyl allyl polyoxyethylene ether and diethylene glycol monobutyl ether maleic anhydride monoester in a molar ratio of 4.5:1:2.5.

[0024] In one specific embodiment, the shrinkage-reducing polycarboxylate superplasticizer comprises acrylic acid, methyl allyl polyoxyethylene ether and diethylene glycol monobutyl ether maleic anhydride monoester in a molar ratio of 4:1.3:2.

[0025] Preferably, the preparation method of the diethylene glycol monobutyl ether maleic anhydride monoester comprises the following steps:

[0026] Maleic anhydride is heated to 53-58℃ to melt completely, then diethylene glycol monobutyl ether is added, stirred and mixed uniformly, heated to 125-135℃, reacted for 4-5h, cooled and purified to obtain diethylene glycol monobutyl ether maleic anhydride monoester;

[0027] In one specific embodiment, the shrinkage-reducing polycarboxylate superplasticizer comprises acrylic acid, methyl allyl polyoxyethylene ether and diethylene glycol monobutyl ether maleic anhydride monoester in a molar ratio of 4:1.3:2.

[0028] By adopting the above technical scheme, the diethylene glycol monobutyl ether maleic anhydride monoester with shrinkage-reducing function is synthesized by esterification reaction of maleic anhydride and diethylene glycol monobutyl ether, and the shrinkage-reducing function is exerted by the diethylene glycol monobutyl ether maleic anhydride monoester, so as to fully synergize the water-reducing effect and the shrinkage-reducing function, thereby improving the strength and durability of the concrete.

[0029] Preferably, the preparation method of the shrinkage-reducing polycarboxylate superplasticizer comprises the following steps:

[0030] S1, dissolve the methyl allyl polyoxyethylene ether in water to obtain a reaction solution, dissolve the acrylic acid and diethylene glycol monobutyl ether maleic anhydride monoester in water to obtain a monomer solution, and dissolve the ammonium persulfate in water to obtain an initiator solution;

[0031] S2, heat the reaction solution to 70-90℃, and drop the monomer solution and the initiator solution into the reaction solution in an inert gas atmosphere, react for 2-2.5h after the dropping is completed, then cool and adjust the pH of the solution to 7-7.5 to obtain the shrinkage-reducing polycarboxylate superplasticizer;

[0032] The total monomer concentration of the methyl allyl polyoxyethylene ether, the acrylic acid and the diethylene glycol monobutyl ether maleic anhydride monoester is 28-32%, and the ammonium persulfate accounts for 0.8-1.2% of the total monomer mass.

[0033] By adopting the above technical scheme, the polycarboxylate superplasticizer is prepared by adopting the free radical polymerization method, and the monomer diethylene glycol monobutyl ether maleic anhydride monoester with shrinkage reduction function is grafted, so that the shrinkage-reducing polycarboxylate superplasticizer is obtained, which has good dispersibility, fully cooperates the water-reducing effect and shrinkage reduction performance, and further significantly improves the strength and durability of the concrete.

[0034] Preferably, the preparation method of the methoxy polyethylene glycol acrylate modified silica comprises the following steps:

[0035] A1, ultrasonic the nanosilica in toluene for 13-15min to obtain a suspension, add the silane coupling agent KH550 into the suspension under an inert gas atmosphere, and heat to 100-110℃, stir for 18-22h, cool to room temperature, and then sequentially perform centrifugation, washing and drying to obtain product 1;

[0036] A2, ultrasonic the product 1 in methanol for 13-15min, add methyl acrylate, heat to 48-52℃, stir for 11-13h, then add ethylenediamine, continue to stir for 11-13h, and finally sequentially perform centrifugation, washing and drying to obtain product 2;

[0037] A3, add the product 2 into dimethyl sulfoxide, stir for 13-15min, heat to 70-80℃, add the methoxy polyethylene glycol acrylate and lithium chloride, stir for 22-24h, then perform centrifugation and washing, and finally dry at 55-60℃ to obtain the methoxy polyethylene glycol acrylate modified silica.

[0038] In a specific embodiment, the weight ratio of nanosilica, silane coupling agent KH550, methyl acrylate, ethylenediamine, methoxy polyethylene glycol acrylate and lithium chloride is 3:9:0.7:1.2:6:0.12.

[0039] In a specific embodiment, the weight ratio of nanosilica, silane coupling agent KH550, methyl acrylate, ethylenediamine, methoxy polyethylene glycol acrylate and lithium chloride is 5:7:0.9:0.9:7:0.1.

[0040] In a specific embodiment, the weight ratio of nanosilica, silane coupling agent KH550, methyl acrylate, ethylenediamine, methoxy polyethylene glycol acrylate and lithium chloride is 2:10:0.5:1.5:5:0.15.

[0041] In a specific embodiment, the weight ratio of nanosilica, silane coupling agent KH550, methyl acrylate, ethylenediamine, methoxy polyethylene glycol acrylate and lithium chloride is 7:5:1.5:0.5:9:0.05.

[0042] When the weight ratio of nanosilica, silane coupling agent KH550, methyl acrylate, ethylenediamine, methoxy polyethylene glycol acrylate and lithium chloride is in the range of (3-5):(7-9):(0.7-0.9):(0.9-1.2):(6-7):(0.1-0.12), the water absorption of the methoxy polyethylene glycol acrylate modified nanosilica applied in concrete is reduced by 0.22-0.48%, the 28d compressive strength is increased by 5.8-7.8MPa, the electric flux is reduced by 110-130C, and the freeze-thaw mass loss rate is reduced by 0.14-0.19%, compared with the methoxy polyethylene glycol acrylate modified nanosilica prepared outside the range, which shows that the ratio range of the components in the methoxy polyethylene glycol acrylate modified nanosilica provided by the application has a good effect on improving the performance of the methoxy polyethylene glycol acrylate modified nanosilica.

[0043] Preferably, the preparation method comprises the following steps: weighing the shrinkage type polycarboxylic acid water reducing agent, methoxy polyethylene glycol acrylate modified nanosilica, sodium dodecyl polyoxyethylene ether sulfonate, coconut diethanolamide, sodium polyacrylate, ammonium polyphosphate, polyether defoamer and water according to the weight parts, and mixing and stirring the above components uniformly to obtain the high-performance concrete admixture composition for wind power tower drums.

[0044] In summary, the application has the following beneficial technical effects:

[0045] 1.The application uses the combination of shrinkage-reducing polycarboxylate superplasticizer, ammonium polyphosphate, sodium polyacrylate and methoxy polyethylene glycol acrylate modified nano-silica to synergistically regulate the hydration process of concrete, slow down the hydration temperature rise, inhibit the generation of cracks and improve the self-repairing ability of concrete, thereby improving the strength and durability of concrete.

[0046] 2.The application uses the combination of triphosphoric acid and sodium polyacrylate to synergistically improve the erosion resistance of concrete and further improve the durability of concrete. DETAILED DESCRIPTION

[0047] The specific embodiments are only an explanation of the application and are not a limitation of the application, and those skilled in the art can make modifications to the embodiments without creative contribution after reading the specification, but as long as the modifications are within the scope of the claims of the application, they are protected by the patent law.

[0048] Material sources

[0049] Acrylic acid, industrial grade (≧99.5%), purchased from Wanhua Chemical Group Co., Ltd.;

[0050] Methylallyl polyoxyethylene ether, TPEG-2400, purchased from Jiangsu Zhongshan Chemical Co., Ltd.;

[0051] Diethylene glycol monobutyl ether, industrial grade (≧99%), purchased from Jiangsu Yida Chemical Co., Ltd.;

[0052] Maleic anhydride, industrial grade (≧99.5%), purchased from Shandong Hongxin Chemical Co., Ltd.;

[0053] Ammonium persulfate, analytical pure (≧98%), purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.;

[0054] Methoxy polyethylene glycol acrylate, MPEGMA-1000, purchased from Wanhua Chemical Group Co., Ltd.;

[0055] Nano-silica, specific surface area 200 m 2 / g, purchased from Wincreate China Investment Co., Ltd.;

[0056] Toluene, industrial grade (≧99%), purchased from China Petroleum Chemical Co., Ltd.;

[0057] Silane coupling agent KH550, purchased from Hubei Xinlantian New Material Co., Ltd.;

[0058] Methanol, industrial grade (≧99.9%), purchased from Shanxi Coking Co., Ltd.;

[0059] Methyl acrylate, industrial grade (≧99%), purchased from Jiangsu Yulong Chemical Co., Ltd.;

[0060] Ethylene diamine, analytical pure (≧99%), purchased from Shanghai Aladdin Biochem Technology Co., Ltd.;

[0061] Dimethyl sulfoxide, pharmaceutical grade (≧99%), purchased from Jiangsu Qiangsheng Functional Chemical Co., Ltd.;

[0062] Lithium chloride, purchased from Jiangxi Gannfon Li Co., Ltd.;

[0063] Sodium dodecyl polyoxyethylene ether sulfonate, industrial grade, purchased from BASF (China) Co., Ltd.;

[0064] Coco-diethanolamide, type 6501 (≧95%), purchased from Nanjing Huatuo Chemical Co., Ltd.;

[0065] Ammonium polyacrylate, industrial grade (molecular weight 8 million), purchased from Shandong Baomo Biological Chemical Co., Ltd.;

[0066] Ammonium tripolyphosphate, industrial grade (≧95%), purchased from Hubei Xingfa Chemical Industry Group Co., Ltd.;

[0067] Polyether defoamer, type TEGO XP22063, purchased from Beijing Kemit Science and Technology Development Co., Ltd.;

[0068] BL-7 polycarboxylic acid water reducer, purchased from Zibo Bailai Building Material Co., Ltd.;

[0069] JC-05 polycarboxylic acid high-performance water reducer, purchased from Shandong Jiangtai New Engineering Materials Group;

[0070] Cement, type P.O52.5, ordinary portland cement, purchased from Anhui Conch Cement Co., Ltd.;

[0071] Fly ash, type I grade, 45 μm residue ≦12%, purchased from Jining Hengzhi New Building Material Co., Ltd.;

[0072] Mineral powder, type S95 grade, 7d activity index ≧75%, purchased from Jining Hengzhi New Building Material Co., Ltd.;

[0073] Sand, river sand, fineness modulus 2.9, clay content ≦1.0%, purchased from Lingshou County Shengbang Mineral Products Co., Ltd.;

[0074] Stone, 5-25 mm continuous gradation, purchased from Shijiazhuang Yuanjing Mineral Products Co., Ltd.;

[0075] Preparation Example 1-1

[0076] The preparation method of diethylene glycol monobutyl ether maleic anhydride monoester includes the following steps:

[0077] Into a three-necked flask equipped with a thermometer, a stirrer and a reflux condenser, 6 moles of maleic anhydride were introduced and heated to 53°C. After complete melting, 2.4 moles of diethylene glycol monobutyl ether were added, the mixture was stirred and heated to 135°C, and reacted for 4 hours. After cooling, the diethylene glycol monobutyl ether maleic anhydride monoester was purified by vacuum filtration.

[0078] Preparation Example 1-2

[0079] The method for preparing the diethylene glycol monobutyl ether maleic anhydride monoester comprises the following steps:

[0080] Into a three-necked flask equipped with a thermometer, a stirrer and a reflux condenser, 8 moles of maleic anhydride were introduced and heated to 58°C. After complete melting, 1.6 moles of diethylene glycol monobutyl ether were added, the mixture was stirred and heated to 125°C, and reacted for 5 hours. After cooling, the diethylene glycol monobutyl ether maleic anhydride monoester was purified by vacuum filtration.

[0081] Preparation Example 2-1

[0082] The method for preparing the reduced shrinkage polycarboxylic acid water reducer comprises the following steps:

[0083] S1, 7200g of methylallyl polyoxyethylene ether was dissolved in water to obtain a reaction solution, 508.2g of acrylic acid and 780g of diethylene glycol monobutyl ether maleic anhydride monoester were dissolved in water to obtain a monomer solution, and 101.9g of ammonium persulfate was dissolved in water to obtain an initiator solution;

[0084] S2, the reaction solution was heated to 70°C, and the monomer solution and the initiator solution were added dropwise into the reaction solution under a nitrogen atmosphere, and after the dropwise addition was completed, the reaction was carried out for 2.5 hours, then the solution was cooled and the pH was adjusted to 7 to obtain a reduced shrinkage polycarboxylic acid water reducer;

[0085] The molar ratio of the methylallyl polyoxyethylene ether, the acrylic acid and the diethylene glycol monobutyl ether maleic anhydride monoester was 4.5:1:2.5, the total monomer concentration of the methylallyl polyoxyethylene ether, the acrylic acid and the diethylene glycol monobutyl ether maleic anhydride monoester was 28%, the ammonium persulfate accounted for 1.2% of the total monomer mass, the total amount of water used in step S1 was 21826.8ml, and the diethylene glycol monobutyl ether maleic anhydride monoester used in step S1 was the diethylene glycol monobutyl ether maleic anhydride monoester prepared in Preparation Example 1-1.

[0086] Preparation Example 2-2

[0087] The method for preparing the reduced shrinkage polycarboxylic acid water reducer comprises the following steps:

[0088] S1, 4800 g of methyl allyl polyoxyethylene ether was dissolved in water to prepare a reaction solution, 653.4 g of acrylic acid and 1300 g of diethylene glycol monobutyl ether maleic anhydride monoester were dissolved in water to prepare a monomer solution, and 54.03 g of ammonium persulfate was dissolved in water to prepare an initiator solution;

[0089] S2, the reaction solution was heated to 90℃, and the monomer solution and the initiator solution were added dropwise into the reaction solution under a nitrogen atmosphere, and after the dropwise addition was completed, the reaction was carried out for 2h, then cooled, and the pH of the solution was adjusted to 7.5 to obtain a shrinkable polycarboxylic acid water reducer;

[0090] The molar ratio of methyl allyl polyoxyethylene ether, acrylic acid and diethylene glycol monobutyl ether maleic anhydride monoester is 3.5:1.5:1.5, the total monomer concentration of methyl allyl polyoxyethylene ether, acrylic acid and diethylene glycol monobutyl ether maleic anhydride monoester is 32%, ammonium persulfate accounts for 0.8% of the total monomer mass, the total amount of water used in step S1 is 14351ml, and the diethylene glycol monobutyl ether maleic anhydride monoester used in step S1 is the diethylene glycol monobutyl ether maleic anhydride monoester prepared in Preparation Example 1-2.

[0091] Preparation Example 2-3

[0092] The difference from Preparation Example 2-1 is that in step S1, the methyl allyl polyoxyethylene ether is 6240g, the acrylic acid is 580.8g, the diethylene glycol monobutyl ether maleic anhydride monoester is 1040g, the ammonium persulfate is 94.33g, the total amount of water used is 20213.5ml, and the molar ratio of methyl allyl polyoxyethylene ether, acrylic acid and diethylene glycol monobutyl ether maleic anhydride monoester is 4:1.3:2.

[0093] Preparation Example 2-4

[0094] The difference from Preparation Example 2-1 is that in step S1, the methyl allyl polyoxyethylene ether is 9600g, the acrylic acid is 435.6g, the diethylene glycol monobutyl ether maleic anhydride monoester is 520g, the ammonium persulfate is 126.7g, the total amount of water used is 27143ml, and the molar ratio of methyl allyl polyoxyethylene ether, acrylic acid and diethylene glycol monobutyl ether maleic anhydride monoester is 3:2:1.

[0095] Preparation Example 2-5

[0096] The difference from Preparation Example 2-1 is that in step S1, the methyl allyl polyoxyethylene ether is 2400g, the acrylic acid is 726g, the diethylene glycol monobutyl ether maleic anhydride monoester is 1560g, the ammonium persulfate is 56.23g, the total amount of water used is 12050ml, and the molar ratio of methyl allyl polyoxyethylene ether, acrylic acid and diethylene glycol monobutyl ether maleic anhydride monoester is 5:0.5:3.

[0097] Preparation Example 3-1

[0098] The preparation method of the methoxypolyethylene glycol acrylate modified silica includes the following steps:

[0099] A1, 600g of nano-silica was added to toluene and ultrasonic treatment was performed for 15min to prepare a suspension. 1800g of silane coupling agent KH550 was added to the suspension under a nitrogen atmosphere, and the temperature was raised to 100°C. After stirring for 22h, the product was cooled to room temperature, and then centrifugation, washing and drying were sequentially performed to obtain product 1;

[0100] A2, product 1 was added to methanol and ultrasonic treatment was performed for 13min. 140g of methyl acrylate was added, and the temperature was raised to 52°C. After stirring for 11h, 240g of ethylenediamine was added, and stirring was continued for 13h. Finally, centrifugation, washing and drying were sequentially performed to obtain product 2;

[0101] A3, product 2 was added to dimethyl sulfoxide, and stirring was performed for 15min. The temperature was raised to 70°C, and 1200g of methoxypolyethylene glycol acrylate and 24g of lithium chloride were added. After stirring for 24h, centrifugation and washing were performed, and finally drying was performed at 55°C to obtain methoxypolyethylene glycol acrylate modified silica.

[0102] Preparation Example 3-2

[0103] The preparation method of the methoxypolyethylene glycol acrylate modified silica includes the following steps:

[0104] A1, 1000g of nano-silica was added to toluene and ultrasonic treatment was performed for 13min to prepare a suspension. 1400g of silane coupling agent KH550 was added to the suspension under a nitrogen atmosphere, and the temperature was raised to 110°C. After stirring for 18h, the product was cooled to room temperature, and then centrifugation, washing and drying were sequentially performed to obtain product 1;

[0105] A2, product 1 was added to methanol and ultrasonic treatment was performed for 15min. 180g of methyl acrylate was added, and the temperature was raised to 48°C. After stirring for 13h, 180g of ethylenediamine was added, and stirring was continued for 11h. Finally, centrifugation, washing and drying were sequentially performed to obtain product 2;

[0106] A3, product 2 was added to dimethyl sulfoxide, and stirring was performed for 13min. The temperature was raised to 80°C, and 1400g of methoxypolyethylene glycol acrylate and 20g of lithium chloride were added. After stirring for 22h, centrifugation and washing were performed, and finally drying was performed at 60°C to obtain methoxypolyethylene glycol acrylate modified silica.

[0107] Preparation Example 3-3

[0108] The difference from Preparation Example 3-1 is that the nano-silica is 400 g, the silane coupling agent KH550 is 2000 g, the methyl acrylate is 100 g, the ethylenediamine is 300 g, the methoxy polyethylene glycol acrylate is 1000 g, and the lithium chloride is 30 g.

[0109] Preparation Example 3-4

[0110] The difference from Preparation Example 3-1 is that the nano-silica is 1400 g, the silane coupling agent KH550 is 1000 g, the methyl acrylate is 300 g, the ethylenediamine is 100 g, the methoxy polyethylene glycol acrylate is 1800 g, and the lithium chloride is 10 g.

[0111] Example 1

[0112] 3500 g of a shrinkage-reducing polycarboxylate superplasticizer, 1200 g of methoxy polyethylene glycol acrylate modified nano-silica, 150 g of sodium dodecyl polyoxyethylene ether sulfonate, 150 g of cocodiethanolamide, 30 g of sodium polyacrylate, 60 g of ammonium tripolyphosphate, 5 g of polyether defoaming agent, and 5000 g of water are mixed and stirred uniformly to prepare a high-performance concrete admixture composition for a wind power tower.

[0113] The shrinkage-reducing polycarboxylate superplasticizer used is the shrinkage-reducing polycarboxylate superplasticizer prepared in Preparation Example 2-1, and the methoxy polyethylene glycol acrylate modified nano-silica is the methoxy polyethylene glycol acrylate modified nano-silica prepared in Preparation Example 3-1.

[0114] Example 2

[0115] 4500 g of a shrinkage-reducing polycarboxylate superplasticizer, 800 g of methoxy polyethylene glycol acrylate modified nano-silica, 250 g of sodium dodecyl polyoxyethylene ether sulfonate, 80 g of cocodiethanolamide, 80 g of sodium polyacrylate, 20 g of ammonium tripolyphosphate, 15 g of polyether defoaming agent, and 4000 g of water are mixed and stirred uniformly to prepare a high-performance concrete admixture composition for a wind power tower.

[0116] The shrinkage-reducing polycarboxylate superplasticizer used is the shrinkage-reducing polycarboxylate superplasticizer prepared in Preparation Example 2-1, and the methoxy polyethylene glycol acrylate modified nano-silica is the methoxy polyethylene glycol acrylate modified nano-silica prepared in Preparation Example 3-1.

[0117] Example 3

[0118] A high-performance concrete admixture composition for a wind power tower drum was prepared by mixing and stirring uniformly 4200 g of a shrinkage-reducing polycarboxylate superplasticizer, 1000 g of methoxy polyethylene glycol acrylate modified nano-silica, 200 g of sodium dodecyl polyoxyethylene ether sulfonate, 100 g of cocodiethanolamide, 60 g of sodium polyacrylate, 40 g of ammonium tripolyphosphate, 10 g of a polyether defoaming agent, and 4390 g of water.

[0119] The shrinkage-reducing polycarboxylate superplasticizer used was the shrinkage-reducing polycarboxylate superplasticizer prepared in Preparation Example 2-1, and the methoxy polyethylene glycol acrylate modified nano-silica used was the methoxy polyethylene glycol acrylate modified nano-silica prepared in Preparation Example 3-1.

[0120] Example 4

[0121] The shrinkage-reducing polycarboxylate superplasticizer used was the shrinkage-reducing polycarboxylate superplasticizer prepared in Preparation Example 2-2.

[0122] Example 5

[0123] The shrinkage-reducing polycarboxylate superplasticizer used was the shrinkage-reducing polycarboxylate superplasticizer prepared in Preparation Example 2-3.

[0124] Example 6

[0125] The shrinkage-reducing polycarboxylate superplasticizer used was the shrinkage-reducing polycarboxylate superplasticizer prepared in Preparation Example 2-4.

[0126] Example 7

[0127] The shrinkage-reducing polycarboxylate superplasticizer used was the shrinkage-reducing polycarboxylate superplasticizer prepared in Preparation Example 2-5.

[0128] Example 8

[0129] The methoxy polyethylene glycol acrylate modified nano-silica used was the methoxy polyethylene glycol acrylate modified nano-silica prepared in Preparation Example 3-2.

[0130] Example 9

[0131] The methoxy polyethylene glycol acrylate modified nano-silica used was the methoxy polyethylene glycol acrylate modified nano-silica prepared in Preparation Example 3-3.

[0132] Example 10

[0133] The difference from Example 3 is that the methoxypolyethylene glycol acrylate modified nano-silica used is the methoxypolyethylene glycol acrylate modified nano-silica prepared in Preparation Example 3-4.

[0134] Comparative Example 1

[0135] The difference from Example 3 is that the shrinkage reducing polycarboxylate superplasticizer used is replaced by a commercially available BL-7 polycarboxylate superplasticizer.

[0136] Comparative Example 2

[0137] The difference from Example 3 is that the shrinkage reducing polycarboxylate superplasticizer used is replaced by a commercially available JC-05 polycarboxylate superplasticizer.

[0138] Application Example 1

[0139] A concrete is prepared by weighing 320 kg of cement, 80 kg of fly ash, 60 kg of mineral powder, 700 kg of sand and 1080 kg of stone, and then adding 128 kg of water and 9.2 kg of the wind power tower concrete admixture composition, and stirring and mixing uniformly. The wind power tower concrete admixture composition used is the wind power tower concrete admixture composition prepared in Example 1.

[0140] Application Examples 2-10

[0141] The difference from Application Example 1 is that the wind power tower concrete admixture composition used is the wind power tower concrete admixture composition prepared in Examples 2-10, respectively.

[0142] Comparative Application Examples 1-2

[0143] The difference from Application Example 1 is that the wind power tower concrete admixture composition used is the wind power tower concrete admixture composition prepared in Comparative Examples 1-2, respectively.

[0144] Performance detection

[0145] The concrete prepared in the above Application Examples 1-10 and Comparative Application Examples 1-2 is respectively made into a concrete test block, and water absorption rate detection, compressive strength detection, chloride ion resistance detection and freeze-thaw cycle detection are carried out.

[0146] 1. Water absorption rate detection: Take a concrete test block of 100 mm x 100 mm x 100 mm, dry it at 105°C for 72 h, and weigh it, denoted as m1. Then immerse the test block in water until the mass is constant, wipe off the surface water, and weigh it again, denoted as m2. The water absorption rate calculation formula is: water absorption rate = (m2-m1) / m1*100%.

[0147] 2. Compressive strength test: The compressive strength of the concrete test block with a size of 150 mm x 150 mm x 150 mm was tested using a pressure testing machine, and the operation was performed in accordance with GB / T 50081-2016 "Standard for Testing Methods of Mechanical Properties of Ordinary Concrete".

[0148] 3. Chloride ion resistance test: The electric flux of the concrete test block with a diameter of 100 mm and a height of 100 mm was tested using a concrete chloride ion electric flux tester, and the operation was performed in accordance with GB / T 50082-2009 "Standard for Testing Methods of Long-term Performance and Durability of Ordinary Concrete".

[0149] 4. Freeze-thaw cycle test: The freeze-thaw cycle test was performed in accordance with GB / T 50082-2009 "Standard for Testing Methods of Long-term Performance and Durability of Ordinary Concrete", the concrete test block with a size of 100 mm x 100 mm x 400 mm was placed in a cycle of -18°C to 4°C, the cycle number was 200 times, and the mass loss rate was measured after the cycle, the mass loss rate = (initial mass - mass after cycle) / initial mass * 100%.

[0150] The performance test results are shown in Table 1.

[0151] Table 1: Concrete performance test results

[0152]

[0153] As can be seen from Table 1, the water absorption rates of the concrete prepared in Application Example 1 and Application Example 2 are 0.87% and 0.93% respectively, the 28d compressive strengths are 82.5 MPa and 81.7 MPa respectively, the electric fluxes are 730 C and 740 C respectively, and the freeze-thaw mass loss rates are 0.63% and 0.67% respectively. Compared with Comparative Application Example 1, the water absorption rates are reduced by 2.25% and 2.19% respectively, the 28d compressive strengths are increased by 22 MPa and 21.2 MPa respectively, the electric fluxes are reduced by 590 C and 580 C respectively, and the freeze-thaw mass loss rates are reduced by 2.1% and 2.06% respectively. Compared with Comparative Application Example 2, the water absorption rates are reduced by 2.19% and 2.13% respectively, the 28d compressive strengths are increased by 21.2 MPa and 20.4 MPa respectively, the electric fluxes are reduced by 550 C and 540 C respectively, and the freeze-thaw mass loss rates are reduced by 1.71% and 1.67% respectively. It is shown that the high-performance concrete admixture composition for wind power tower provided in the embodiments 1 and 2 has a significant effect on improving the strength and durability of the concrete.

[0154] The water absorption of the concrete prepared in application example 3 is reduced by 0.09% and 0.15% respectively compared with application examples 1 and 2, the 28d compressive strength is increased by 2.7MPa and 3.5MPa respectively, the electric flux is reduced by 20C and 30C respectively, and the freeze-thaw mass loss rate is reduced by 0.07% and 0.11% respectively, which indicates that the preferred ratio of the high-performance concrete admixture composition for wind power tower provided in application example 3 can make the components fully play a synergistic effect, thereby further improving the strength and durability of the concrete.

[0155] The data in application example 4 are close to the data in application example 3, which indicates that the preferred ratio of the shrinkage-reducing polycarboxylate superplasticizer provided in the application has a good effect on improving the strength and durability of the concrete.

[0156] The water absorption of the concrete prepared in application example 5 is reduced by 0.06% compared with application example 3, the 28d compressive strength is increased by 3.4MPa, the electric flux is reduced by 110C, and the freeze-thaw mass loss rate is reduced by 0.14%, which indicates that the preferred ratio of the components in the shrinkage-reducing polycarboxylate superplasticizer provided in the application has a good effect on the synergistic effect of further improving the shrinkage-reducing effect and water-reducing performance of the shrinkage-reducing polycarboxylate superplasticizer.

[0157] The water absorption of the concrete prepared in application examples 6 and 7 is increased by 0.85% and 1.07% respectively compared with application example 3, the 28d compressive strength is reduced by 12MPa and 13.7MPa respectively, the electric flux is increased by 210C and 240C respectively, and the freeze-thaw mass loss rate is increased by 0.39% and 0.57% respectively, which indicates that the ratio range of the components in the shrinkage-reducing polycarboxylate superplasticizer provided in the application has a good effect on the synergistic effect of improving the shrinkage-reducing effect and water-reducing performance of the shrinkage-reducing polycarboxylate superplasticizer.

[0158] The data in application example 8 are close to the data in application example 3, which indicates that the ratio range of the methoxy polyethylene glycol acrylate modified nano silicon dioxide provided in the application has a good effect on improving the strength and durability of the concrete.

[0159] The water absorption of the concrete prepared in application examples 9 and 10 is increased by 0.25% and 0.48% respectively compared with application example 3, the 28d compressive strength is reduced by 6.9MPa and 7.8MPa respectively, the electric flux is increased by 130C and 110C respectively, and the freeze-thaw mass loss rate is increased by 0.19% and 0.15% respectively, which indicates that the ratio range of the components in the methoxy polyethylene glycol acrylate modified nano silicon dioxide provided in the application has a good effect on improving the performance of the methoxy polyethylene glycol acrylate modified nano silicon dioxide.

[0160] The water absorption of the concrete prepared in Comparative Application Example 1 and Comparative Application Example 2 compared with Application Example 3 is increased by 2.34% and 2.28% respectively, the 28d compressive strength is reduced by 24.7MPa and 23.9MPa respectively, the electric flux is increased by 610C and 570C respectively, the freeze-thaw mass loss rate is increased by 2.17% and 1.78% respectively, which shows that the shrinkage-reducing polycarboxylate superplasticizer provided in the application has a more excellent effect on improving the strength and durability of concrete compared with other commercially available polycarboxylate superplasticizers.

Claims

1. A high performance concrete admixture composition for wind turbine towers, characterized by, The composition comprises the following components in parts by weight: 35-45 parts of a shrinkage-reducing polycarboxylic acid water reducer, 8-12 parts of methoxy polyethylene glycol acrylate modified nano silicon dioxide, 1.5-2.5 parts of sodium dodecyl polyoxyethylene ether sulfonate, 0.8-1.5 parts of coconut diethanolamide, 0.3-0.8 parts of sodium polyacrylate, 0.2-0.6 parts of ammonium tripolyphosphate, 0.05-0.15 parts of polyether defoamer, and 40-50 parts of water; the preparation method of the methoxy polyethylene glycol acrylate modified nano silicon dioxide comprises the following steps: A1, nano silicon dioxide is added to toluene, ultrasonic is performed for 13-15 min to prepare a suspension, silane coupling agent KH550 is added to the suspension under an inert gas atmosphere, and the temperature is raised to 100-110 DEG C, stirring is performed for 18-22 h, after cooling to room temperature, centrifugation, washing and drying are sequentially performed to obtain product 1; A2, product 1 is added to methanol, ultrasonic is performed for 13-15 min, methyl acrylate is added, the temperature is raised to 48-52 DEG C, stirring is performed for 11-13 h, then ethylenediamine is added, stirring is continued for 11-13 h, and finally centrifugation, washing and drying are sequentially performed to obtain product 2; A3, product 2 is added to dimethyl sulfoxide, stirring is performed for 13-15 min, the temperature is raised to 70-80 DEG C, methoxy polyethylene glycol acrylate and lithium chloride are added, stirring is performed for 22-24 h, then centrifugation and washing are performed, and finally drying is performed at 55-60 DEG C to obtain methoxy polyethylene glycol acrylate modified nano silicon dioxide; wherein the weight ratio of nano silicon dioxide, silane coupling agent KH550, methyl acrylate, ethylenediamine, methoxy polyethylene glycol acrylate and lithium chloride is (3-5):(7-9):(0.7-0.9):(0.9-1.2):(6-7):(0.1-0.12).

2. The high performance concrete admixture composition for a wind power tower according to claim 1, characterized by, The composition comprises the following components in parts by weight: 42 parts of a shrinkage-reducing polycarboxylic acid water reducer, 10 parts of methoxy polyethylene glycol acrylate modified nano silicon dioxide, 2 parts of sodium dodecyl polyoxyethylene ether sulfonate, 1 part of coconut diethanolamide, 0.6 parts of sodium polyacrylate, 0.4 parts of ammonium tripolyphosphate, 0.1 parts of polyether defoamer, and 43.9 parts of water.

3. The high performance concrete admixture composition for wind tower according to claim 1, characterized in that: The shrinkage-reducing polycarboxylic acid water reducer comprises acrylic acid, methyl allyl polyoxyethylene ether and diethylene glycol monobutyl ether maleic anhydride monoester in a molar ratio of (3.5-4.5):(1-1.5):(1.5-2.5).

4. A high performance concrete admixture composition for wind tower according to claim 3, characterized in that: The shrinkage-reducing polycarboxylic acid water reducer comprises acrylic acid, methyl allyl polyoxyethylene ether and diethylene glycol monobutyl ether maleic anhydride monoester in a molar ratio of 4:1.3:

2.

5. The high performance concrete admixture composition for wind tower according to claim 3, characterized in that, The preparation method of the diethylene glycol monobutyl ether maleic anhydride monoester comprises the following steps: maleic anhydride is heated to 53-58 DEG C to melt completely, then diethylene glycol monobutyl ether is added, stirring is performed until mixed uniformly, and heating is performed to 125-135 DEG C, reaction is performed for 4-5 h, cooling and purification are performed to obtain diethylene glycol monobutyl ether maleic anhydride monoester; wherein the molar ratio of maleic anhydride to diethylene glycol monobutyl ether is (3-4):(0.8-1.2).

6. A high performance concrete admixture composition for wind turbine towers according to claim 5, characterized in that, The preparation method of the reduced polycarboxylic acid water reducing agent comprises the following steps: S1, dissolving methyl allyl polyoxyethylene ether in water to obtain a reaction solution, dissolving acrylic acid and diethylene glycol monobutyl ether maleic anhydride monoester in water to obtain a monomer solution, and dissolving ammonium persulfate in water to obtain an initiator solution; S2, heating the reaction solution to 70-90 DEG C, adding the monomer solution and the initiator solution dropwise into the reaction solution in an inert gas atmosphere, reacting for 2-2.5 h after the dropwise addition is completed, then cooling, and adjusting the pH of the solution to 7-7.5 to obtain the reduced polycarboxylic acid water reducing agent; wherein the total monomer concentration of methyl allyl polyoxyethylene ether, acrylic acid and diethylene glycol monobutyl ether maleic anhydride monoester is 28-32%, and ammonium persulfate accounts for 0.8-1.2% of the total monomer mass.

7. A method of preparing a high performance concrete admixture composition for wind turbine towers according to any one of claims 1 to 6, characterized in that, The preparation method comprises the following steps: weighing the reduced polycarboxylic acid water reducing agent, methoxy polyethylene glycol acrylate modified nano silicon dioxide, sodium dodecyl polyoxyethylene ether sulfonate, cocodiethanolamide, sodium polyacrylate, ammonium polyphosphate, polyether defoaming agent and water according to weight parts, and uniformly mixing and stirring the above components to obtain a high-performance concrete admixture composition for a wind power tower drum.

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