Unshaped refractory material as well as preparation method and application thereof

Abstract

The invention discloses an unshaped refractory material as well as a preparation method and application thereof, and relates to the technical field of refractory materials. The unshaped refractory material comprises the following raw materials in parts by weight: 60-80 parts of refractory aggregate, 25-35 parts of powder, 8-10 parts of a binding agent and 0.5-1 part of a water reducing agent. The unshaped refractory material prepared by the invention has excellent mechanical properties, slag resistance and thermal shock resistance, and has important application significance in industrial kilns.

Description

An unshaped refractory material, its preparation method and application Technical Field

[0001] This invention relates to the field of refractory materials technology, specifically to an unshaped refractory material, its preparation method, and its application. Background Technology

[0002] Unshaped refractories, due to their advantages such as convenient construction, good integrity, and controllable cost, have been widely used in key lining components of high-temperature industrial kilns in steel, cement, and glass industries (e.g., ladles, rotary kilns, and heating furnaces). Their performance depends on raw material matching, bonding system, and microstructure design. The binder, acting as a bridge between aggregates and powders, directly affects the material's strength, medium- and high-temperature stability, corrosion resistance, and service life. Currently used binders can be broadly classified into inorganic binders (such as calcium aluminate cement, phosphates, and silicates) and organic binders (such as phenolic resins and epoxy resins). However, traditional inorganic binders have slow curing speeds at room temperature, limited interfacial bonding with aggregates, and are prone to structural embrittlement or reaction with slag under high-temperature conditions. While traditional organic binders such as phenolic resins can provide medium-temperature strength through carbonization, their low residual carbon content and high brittleness prevent them from forming a stable ceramic bond. Therefore, developing a novel binder that combines high adhesion at room temperature, erosion resistance at medium and high temperatures, and good thermal shock stability is of great significance for overcoming the performance defects of existing monolithic refractory materials.

[0003] Chinese invention patent CN107721439A discloses an unshaped refractory material and its preparation method. The main raw materials include silicon dioxide, aluminum oxide, calcium oxide, and magnesium oxide; the auxiliary raw materials include at least one of ferrous oxide, titanium dioxide, and chromium oxide. This unshaped refractory material utilizes recycled waste materials, such as red mud, copper slag, laterite nickel ore, and chromite, resulting in lower costs compared to commercially available special refractory materials. When this unshaped refractory material is laid as the lining of a melting device at temperatures above 1500°C, and is used in a hot state exposed to gases containing acidic or alkaline components or in a molten environment, it exhibits a glassy state, effectively preventing contact between molten materials and the lining refractory material within the melting device. This significantly protects the lining refractory material and improves the service life of the melting device. However, its thermal shock resistance is still insufficient. Summary of the Invention

[0004] In view of the shortcomings of the existing technology, the purpose of this invention is to provide an unshaped refractory material, its preparation method and application.

[0005] To achieve the above objectives, the present invention provides the following technical solution: an unshaped refractory material comprising the following raw materials in parts by weight: 60-80 parts refractory aggregate, 25-35 parts powder, 8-10 parts binder, and 0.5-1 parts water-reducing agent; the binder is prepared by the following method: S1: glycidyl methacrylate reacts with furanoic acid to generate intermediate 1, the reaction equation of which is shown below: .

[0006] S2: Intermediate 1 reacts with 3-glycidyl etheroxypropyltriethoxysilane to generate intermediate 2, as shown in the following reaction equation: .

[0007] S3: Intermediate 2 reacts with pinacol 4-chloromethylphenylboronic acid ester to generate intermediate 3, and the reaction equation is shown below: .

[0008] S4: Intermediate 3 reacts with ((3,13-diundecyl-2,14-dioxa-5,11-diazapentadecanoyl)bis(butane-2,1,4-triyl))tetraphosphonic acid to form a binder, and the reaction equation is shown below: .

[0009] In step S1, the molar ratio of glycidyl methacrylate to furanoic acid is 1:(1.05-1.1).

[0010] In step S2, the molar ratio of intermediate 1 to 3-glycidyl etheroxypropyltriethoxysilane is 1:(1.05-1.1).

[0011] In step S3, the molar ratio of intermediate 2 to pinacol 4-chloromethylphenylboronic acid is 1:(1.1-1.2).

[0012] In step S4, the molar ratio of intermediate 3 to ((3,13-diundecyl-2,14-dioxa-5,11-diazapentadecanoyl)bis(butane-2,1,4-triyl))tetraphosphonic acid is (2.1-2.2):1.

[0013] The refractory aggregate includes magnesium aluminum spinel and silica, wherein the magnesium aluminum spinel accounts for 60% by weight and the silica accounts for 40% by weight.

[0014] The powder includes SiO2 micro powder and fly ash, wherein the weight percentage of SiO2 micro powder is 40% and the weight percentage of fly ash is 60%.

[0015] The water-reducing agent is a polycarboxylate high-performance water-reducing agent.

[0016] A method for preparing an unshaped refractory material includes the following steps: (1) weighing 60-80 parts of refractory aggregate, 25-35 parts of powder, 8-10 parts of binder, and 0.5-1 parts of water-reducing agent by weight; (2) drying the refractory aggregate and powder to obtain pretreated refractory aggregate and powder; and mixing the pretreated refractory aggregate, powder, binder, and water-reducing agent to obtain an unshaped refractory material.

[0017] Application of an amorphous refractory material in industrial kilns.

[0018] Due to the adoption of the above technical solutions, the beneficial effects of the present invention include: the unshaped refractory material prepared by the present invention has excellent mechanical properties, slag resistance and thermal shock resistance, wherein the added binder has phosphonate, siloxane segments, borate esters, long-chain alkyl and furan ring structures, which exhibit a significant synergistic enhancement effect in the unshaped refractory material system. Detailed Implementation

[0019] The following description, in conjunction with specific embodiments, provides further details, but the present invention is not limited to these embodiments.

[0020] Example 1: Preparation of ((3,13-diundecyl-2,14-dioxa-5,11-diazapentadecanoyl)bis(butane-2,1,4-triyl))tetraphosphonic acid: Under nitrogen protection, 250 ml of anhydrous acetonitrile, 0.1 mol of 1,5-diaminopentane, and 0.205 mol of 2-undecyl ethylene oxide were stirred and mixed. The mixture was heated to 60 °C and reacted for 5 h. After cooling to room temperature, the mixture was distilled under reduced pressure at 50 °C for 1 h. 200 ml of cold anhydrous n-hexane was added and stirred to precipitate the precipitate. The precipitate was filtered, washed with cold anhydrous n-hexane (3 × 50 ml), and dried under vacuum at 50 °C for 8 h to obtain intermediate A. The reaction equation is shown below: .

[0021] Its 1H NMR data are as follows: 1¹H NMR (400 MHz, DMSO-d⁶) δ 4.51 (d, J = 4.9 Hz, 2H), 3.61 (d, J = 5.0 Hz, 2H), 2.77 (s, 2H), 2.71–2.58 (m, 8H), 1.54–1.24 (m, 46H), 0.89 (s, 6H); N₂: Under nitrogen protection, 1000 mL of anhydrous tetrahydrofuran, 0.21 mol of 4-phosphono-2-(phosphonomethyl)-butyric acid, 0.5 mol of benzyl bromide, and 0.3 mol of potassium carbonate were mixed and stirred at room temperature for 10 h. After filtration, 0.1 mol of intermediate A and 0.1 mol of 1-hydroxybenzotriazole were added and stirred until well mixed. Then, 0.21 mol of dicyclohexylcarbodiimide and 0.04 mol of... 4-Dimethylaminopyridine was reacted at 25°C for 18 h, filtered, and 1200 ml of cold anhydrous n-hexane was added to the filtrate and stirred to precipitate. The precipitate was filtered, and the filter cake was washed with cold anhydrous n-hexane (3 × 120 ml). 500 ml of tetrahydrofuran was added and stirred to dissolve the precipitate. 0.5 g of 10 wt% Pd / C was added, and the mixture was stirred at room temperature for 12 h under a hydrogen atmosphere (0.3 MPa). The mixture was filtered, and the filtrate was rotary evaporated at 45°C for 2 h and dried under vacuum at 60°C for 12 h to obtain ((3,13-diundecyl-2,14-dioxa-5,11-diazapentadecanoyl)bis(butane-2,1,4-triyl))tetraphosphonic acid. The reaction equation is shown below: .

[0022] Its 1H NMR data are as follows: 1 H NMR (400 MHz, DMSO-d6) δ 8.61 (s, 4H), 8.43 (s,4H), 4.30 (s, 2H), 3.04-2.99 (m, 2H), 2.91 (d, J = 0.6 Hz, 4H), 2.73 (s, 2H), 2.69 (d, J = 0.5 Hz, 4H), 2.44-1.24 (m, 58H), 0.89 (s, 6H).

[0023] Example 2 Preparation of the binder: S1: Under nitrogen protection, 200 ml of anhydrous acetonitrile, 0.1 mol of glycidyl methacrylate, and 0.105 mol of furanoic acid were stirred and mixed. 0.011 mol of tetraethylammonium bromide and 0.11 mol of triethylamine were added, and the mixture was heated to 60 °C and reacted for 6 h. After cooling to room temperature, the mixture was filtered, and the filtrate was transferred to a separatory funnel and washed with 5 wt% sodium bicarbonate solution (3 × 100 ml) to separate the organic phase. The organic phase was washed with deionized water until neutral, and distilled under reduced pressure at 50 °C for 1 h. 150 ml of cold diethyl ether was added and stirred to precipitate the precipitate. The precipitate was filtered, and the filter cake was washed with cold diethyl ether (3 × 50 ml) and dried under vacuum at 60 °C for 8 h to obtain intermediate 1. Its 1H NMR data are as follows: 1 ¹H NMR (400MHz, DMSO-d⁶) δ 7.85 (s, 1H), 7.30 (s, 1H), 6.67 (s, 1H), 5.85 (dd, J = 10.3, 12.4 Hz, 2H), 5.17 (d, J = 5.0 Hz, 1H), 4.35–4.01 (m, 5H), 1.90 (s, 3H); S₂: Under nitrogen protection, 350 ml anhydrous DMF, 0.1 mol intermediate 1, 0.105 mol 3-glycidyl etheroxypropyltriethoxysilane, and 8 g 4A molecular sieve was stirred and mixed thoroughly. 0.011 mol tetraethylammonium bromide and 0.11 mol triethylamine were added, and the mixture was heated to 60°C and reacted for 8 hours. After cooling to room temperature, the mixture was filtered and concentrated under reduced pressure at 60°C for 2 hours to obtain a concentrated solution. Under ice bath conditions, 300 ml of a mixed solution of anhydrous n-hexane and anhydrous ethyl acetate (V) was slowly added to the concentrated solution. 无水正己烷 :V 无水乙酸乙酯 =9:1), stir to precipitate, filter, wash the filter cake with cold anhydrous n-hexane (3 × 50 ml), and then wash with a mixed solution of anhydrous n-hexane and anhydrous ethyl acetate (V 无水正己烷 :V 无水乙酸乙酯 Recrystallization of (9:1) and vacuum drying at 60℃ for 8 hours yielded intermediate 2; its 1H NMR data are as follows: 1HNMR (400 MHz, DMSO-d6) δ 7.85 (s, 1H), 7.30 (s, 1H), 6.67 (s, 1H), 5.85 (dd,J = 10.3, 12.4 Hz, 2H), 4.88 (d, J = 5.0 Hz, 1H), 4.32-4.08 (m, 5H), 3.90 (d,J = 5.0 Hz, 1H), 3.65-3.33 (m, 12H), 1.90 (s, 3H), 1.69 (d, J = 1.1 Hz, 2H), 1.28 (d, J = 12.4 Hz, 2H), 1.20 (s, 9H); S3: Under nitrogen protection, 400 ml of anhydrous DMF, 0.1 mol of intermediate 2, 0.11 mol of 4-chloromethylphenylboronic acid pinacol ester, and 10 g of 4A molecular sieve were stirred and mixed. 0.012 mol of tetraethylammonium bromide and 0.12 mol of K3PO4 were added, and the mixture was heated to 55 °C and reacted for 5 h. After cooling to room temperature, the mixture was filtered and concentrated under reduced pressure at 60 °C for 2 h to obtain a concentrated solution. Under ice bath conditions, 400 ml of cold anhydrous diethyl ether was slowly added to the concentrated solution and stirred to precipitate the precipitate. The precipitate was filtered, and the filter cake was washed with cold anhydrous diethyl ether (3 × 80 ml). The precipitate was then washed with a mixed solution of anhydrous diethyl ether and anhydrous ethyl acetate (V 无水乙醚 :V 无水乙酸乙酯 Recrystallization of (9:1) and vacuum drying at 60℃ for 8 hours yielded intermediate 3; its 1H NMR data are as follows: 1H NMR (400 MHz, DMSO-d6) δ 7.85 (s, 1H), 7.66-7.58 (m, 2H), 7.30 (s, 1H), 7.25-7.17 (m, 2H), 6.67 (s, 1H), 5.85 (dd, J = 10.3, 12.4 Hz, 2H), 4.66-4.51 (m, 2H), 4.32-4.07 (m, 5H), 4.00 (s, 1H), 3.65-3.39 (m, 12H), 1.90 (s, 3H), 1.69 (d, J = 0.5 Hz, 2H), 1.34 (d, J = 10.1 Hz, 12H), 1.28 (d, J =12.4 Hz, 2H), 1.20 (s, 9H); S4: Under nitrogen protection, 1000 ml of anhydrous tetrahydrofuran, 0.21 mol of intermediate 3, 0.1 mol of ((3,13-diundecyl-2,14-dioxa-5,11-diazapentadecanoyl)bis(butane-2,1,4-triyl))tetraphosphonic acid, 0.01 mol of 1,8-diazabicycloundec-7-ene, and 5 mmol of hydroquinone were stirred and mixed, and the mixture was heated to 50 °C and reacted for 10 h; cooled to room temperature, and distilled under reduced pressure at 40 °C for 1 h. Under ice bath, 600 ml of cold anhydrous n-hexane was slowly added and stirred to precipitate the precipitate. The precipitate was filtered, and the filter cake was washed with cold anhydrous n-hexane (3 × 100 ml), and then washed with a mixed solution of anhydrous n-hexane and anhydrous ethyl acetate (V 无水乙醚 :V 无水乙酸乙酯 The mixture was recrystallized from a concentration of 8:2 and dried under vacuum at 50°C for 10 hours to obtain the binder; its 1H NMR data are as follows: 1 H NMR (400 MHz, DMSO-d6)δ 8.61 (s, 4H), 8.43 (s, 4H), 7.85 (s, 2H), 7.66-7.58 (m, 4H), 7.30 (s, 2H),7.24-7.17 (m, 4H), 6.67 (s, 2H), 4.66-4.50 (m, 6H), 4.33-4.09 (m, 10H), 4.00(s, 2H), 3.63-3.40 (m, 24H), 2.87-1.24 (m, 106H), 1.20 (s, 18H), 1.11 (s,6H), 0.89 (s, 6H).

[0024] Example 3 Preparation of the binder: S1: Under nitrogen protection, 200 ml of anhydrous acetonitrile, 0.1 mol of glycidyl methacrylate, and 0.108 mol of furanoic acid were stirred and mixed. 0.011 mol of tetraethylammonium bromide and 0.11 mol of triethylamine were added. The mixture was heated to 55 °C and reacted for 5 h. After cooling to room temperature, the mixture was filtered. The filtrate was transferred to a separatory funnel and washed with 5 wt% sodium bicarbonate solution (3 × 100 ml) to separate the organic phase. The organic phase was washed with deionized water until neutral and distilled under reduced pressure at 50 °C for 1 h. 150 ml of cold diethyl ether was added and stirred to precipitate the precipitate. The precipitate was filtered, and the filter cake was washed with cold diethyl ether (3 × 50 ml) and dried under vacuum at 60 °C for 8 h to obtain intermediate 1; S2: Under nitrogen protection, 350 ml of anhydrous DMF, 0.1 mol of intermediate 1, 0.108 mol of 3-glycidyl etheroxypropyltriethoxysilane, and 8 g of... 4A molecular sieve was stirred and mixed thoroughly. 0.011 mol tetraethylammonium bromide and 0.11 mol triethylamine were added, and the mixture was heated to 65°C and reacted for 7 hours. After cooling to room temperature, the mixture was filtered and concentrated under reduced pressure at 60°C for 2 hours to obtain a concentrated solution. Under ice bath conditions, 300 ml of a mixed solution of anhydrous n-hexane and anhydrous ethyl acetate (V) was slowly added to the concentrated solution. 无水正己烷 :V 无水乙酸乙酯 =9:1), stir to precipitate, filter, wash the filter cake with cold anhydrous n-hexane (3 × 50 ml), and then wash with a mixed solution of anhydrous n-hexane and anhydrous ethyl acetate (V 无水正己烷 :V 无水乙酸乙酯 =9:1) recrystallized, dried under vacuum at 60℃ for 8h to obtain intermediate 2; S3: under nitrogen protection, 400ml anhydrous DMF, 0.1mol intermediate 2, 0.115mol 4-chloromethylphenylboronic acid pinacol ester, and 10g 4A molecular sieve were stirred and mixed, 0.012mol tetraethylammonium bromide and 0.12mol K3PO4 were added, the temperature was raised to 55℃ and reacted for 5h, cooled to room temperature, filtered, concentrated under reduced pressure at 60℃ for 2h to obtain concentrated solution, under ice bath, 400ml cold anhydrous diethyl ether was slowly added to concentrated solution and stirred to precipitate, filtered, the filter cake was washed with cold anhydrous diethyl ether (3×80ml), and washed with a mixed solution of anhydrous diethyl ether and anhydrous ethyl acetate (V 无水乙醚 :V 无水乙酸乙酯=9:1) recrystallized and dried under vacuum at 60℃ for 8h to obtain intermediate 3; S4: Under nitrogen protection, 1000ml of anhydrous tetrahydrofuran, 0.215mol of intermediate 3, 0.1mol of ((3,13-diundecyl-2,14-dioxa-5,11-diazapentadecanoyl)bis(butane-2,1,4-triyl))tetraphosphonic acid, 0.01mol of 1,8-diazabicycloundec-7-ene, and 5mmol of hydroquinone were stirred and mixed, and the mixture was heated to 55℃ for 9h; cooled to room temperature, and distilled under reduced pressure at 40℃ for 1h. Under ice bath conditions, 600ml of cold anhydrous n-hexane was slowly added and stirred to precipitate the precipitate. The precipitate was filtered, and the filter cake was washed with cold anhydrous n-hexane (3×100ml), and then washed with a mixed solution of anhydrous n-hexane and anhydrous ethyl acetate (V 无水乙醚 :V 无水乙酸乙酯 The binder was obtained by recrystallizing (8:2 ratio) and vacuum drying at 50°C for 10 hours.

[0025] Example 4 Preparation of the binder: S1: Under nitrogen protection, 200 ml of anhydrous acetonitrile, 0.1 mol of glycidyl methacrylate, and 0.11 mol of furanoic acid were stirred and mixed. 0.011 mol of tetraethylammonium bromide and 0.11 mol of triethylamine were added, and the mixture was heated to 70 °C and reacted for 4 h. After cooling to room temperature, the mixture was filtered, and the filtrate was transferred to a separatory funnel and washed with 5 wt% sodium bicarbonate solution (3 × 100 ml) to separate the organic phase. The organic phase was washed with deionized water until neutral, and distilled under reduced pressure at 50 °C for 1 h. 150 ml of cold diethyl ether was added and stirred to precipitate the precipitate. The precipitate was filtered, and the filter cake was washed with cold diethyl ether (3 × 50 ml) and dried under vacuum at 60 °C for 8 h to obtain intermediate 1; S2: Under nitrogen protection, 350 ml of anhydrous DMF, 0.1 mol of intermediate 1, 0.11 mol of 3-glycidyl etheroxypropyltriethoxysilane, and 8 g of... 4A molecular sieve was stirred and mixed thoroughly. 0.011 mol tetraethylammonium bromide and 0.11 mol triethylamine were added, and the mixture was heated to 70°C and reacted for 6 hours. After cooling to room temperature, the mixture was filtered and concentrated under reduced pressure at 60°C for 2 hours to obtain a concentrated solution. Under ice bath conditions, 300 ml of a mixed solution of anhydrous n-hexane and anhydrous ethyl acetate (V) was slowly added to the concentrated solution. 无水正己烷 :V 无水乙酸乙酯 =9:1), stir to precipitate, filter, wash the filter cake with cold anhydrous n-hexane (3 × 50 ml), and then wash with a mixed solution of anhydrous n-hexane and anhydrous ethyl acetate (V 无水正己烷 :V 无水乙酸乙酯=9:1) recrystallized, dried under vacuum at 60℃ for 8h to obtain intermediate 2; S3: under nitrogen protection, 400ml anhydrous DMF, 0.1mol intermediate 2, 0.12mol 4-chloromethylphenylboronic acid pinacol ester, and 10g 4A molecular sieve were stirred and mixed, 0.012mol tetraethylammonium bromide and 0.12mol K3PO4 were added, the temperature was raised to 60℃ and reacted for 4h, cooled to room temperature, filtered, concentrated under reduced pressure at 60℃ for 2h to obtain concentrated solution, under ice bath, 400ml cold anhydrous diethyl ether was slowly added to concentrated solution and stirred to precipitate, filtered, the filter cake was washed with cold anhydrous diethyl ether (3×80ml), and washed with a mixed solution of anhydrous diethyl ether and anhydrous ethyl acetate (V 无水乙醚 :V 无水乙酸乙酯 =9:1) recrystallized and dried under vacuum at 60℃ for 8h to obtain intermediate 3; S4: Under nitrogen protection, 1000ml of anhydrous tetrahydrofuran, 0.22mol of intermediate 3, 0.1mol of ((3,13-diundecyl-2,14-dioxa-5,11-diazapentadecanoyl)bis(butane-2,1,4-triyl))tetraphosphonic acid, 0.01mol of 1,8-diazabicycloundec-7-ene, and 5mmol of hydroquinone were stirred and mixed, and the mixture was heated to 60℃ for 8h; cooled to room temperature, and distilled under reduced pressure at 40℃ for 1h. Under ice bath, 600ml of cold anhydrous n-hexane was slowly added and stirred to precipitate the precipitate. The precipitate was filtered, and the filter cake was washed with cold anhydrous n-hexane (3×100ml), and then washed with a mixed solution of anhydrous n-hexane and anhydrous ethyl acetate (V 无水乙醚 :V 无水乙酸乙酯 The binder was obtained by recrystallizing (8:2 ratio) and vacuum drying at 50°C for 10 hours.

[0026] Example 5 Preparation of unshaped refractory material: (1) Weigh the following by weight: 600g of refractory aggregate (360g of magnesium aluminum spinel, 240g of silica), 250g of powder (100g of SiO2 micro powder, 150g of fly ash), 80g of binder (prepared in Example 2), and 5g of water-reducing agent (polycarboxylate high-performance water-reducing agent); (2) Place magnesium aluminum spinel, silica, SiO2 micro powder, and fly ash in an oven at 110℃ and dry for 24h to obtain pretreated refractory aggregate and powder; add the pretreated refractory aggregate, powder, binder, and water-reducing agent to a mixer and stir at 200rpm for 30min to obtain unshaped refractory material.

[0027] Example 6 Preparation of unshaped refractory material: (1) Weigh the following by weight: 700g of refractory aggregate (420g of magnesium aluminum spinel, 280g of silica), 300g of powder (120g of SiO2 micro powder, 180g of fly ash), 90g of binder (prepared in Example 3), and 8g of water-reducing agent (polycarboxylate high-performance water-reducing agent); (2) Place magnesium aluminum spinel, silica, SiO2 micro powder, and fly ash in an oven at 110℃ and dry for 24h to obtain pretreated refractory aggregate and powder; add the pretreated refractory aggregate, powder, binder, and water-reducing agent to a mixer and stir at 200rpm for 30min to obtain unshaped refractory material.

[0028] Example 7 Preparation of unshaped refractory material: (1) Weigh the following by weight: 800g of refractory aggregate (480g of magnesium aluminum spinel, 320g of silica), 350g of powder (140g of SiO2 micro powder, 210g of fly ash), 100g of binder (prepared in Example 4), and 10g of water-reducing agent (polycarboxylate high-performance water-reducing agent); (2) Place magnesium aluminum spinel, silica, SiO2 micro powder, and fly ash in an oven at 110℃ and dry for 24h to obtain pretreated refractory aggregate and powder; add the pretreated refractory aggregate, powder, binder, and water-reducing agent to a mixer and stir at 200rpm for 30min to obtain unshaped refractory material.

[0029] The raw material composition and preparation method of the unshaped refractory material in Comparative Example 1 are basically the same as those in Example 6. The difference is that the binder is replaced with an equal weight of binder prepared by the following method: The preparation method of the binder is basically the same as that in Example 3. The difference is that 3-glycidyl etheroxypropyltriethoxysilane in step S2 is replaced with an equal molar amount of 3-glycidyl etheroxypropylmethyldiethoxysilane.

[0030] The raw material composition and preparation method of the unshaped refractory material in Comparative Example 2 are basically the same as those in Example 6. The difference is that the binder is replaced with an equal weight of binder prepared by the following method: The preparation method of the binder is basically the same as that in Example 3. The difference is that intermediate 3 in step S4 is replaced with an equimolar amount of intermediate 2 (prepared in step S2 of Example 3).

[0031] The raw material composition and preparation method of the unshaped refractory material in Comparative Example 3 are basically the same as those in Example 6, except that the binder is replaced with an equal weight of binder prepared by the following method: The preparation method of the binder is basically the same as that in Example 3, except that the ((3,13-diundecyl-2,14-dioxa-5,11-diazapentadecanoyl)bis(butane-2,1,4-triyl))tetraphosphonic acid in step S4 is replaced with 0.2 mol of 2-{[(1-(hexylamino)tridecane-2-yl)oxy]carbonyl}butane-1,4-diylbisphosphonic acid; 2-{[(1-(hexylamino)tridecane-2-yl)oxy]carbonyl}butane-1,4-diylbisphosphonic acid is prepared by the following method: N1: Under nitrogen protection, 250 ml of anhydrous acetonitrile, 0.2 mol of n-hexylamine, and 0.205 mol of... 2-Undecylethylene oxide was stirred and mixed thoroughly, then heated to 60℃ and reacted for 5 h. After cooling to room temperature, it was distilled under reduced pressure at 50℃ for 1 h. 200 ml of cold anhydrous n-hexane was added and stirred to precipitate the mixture. The precipitate was filtered, and the filter cake was washed with cold anhydrous n-hexane (3 × 50 ml). The mixture was then dried under vacuum at 50℃ for 8 h to obtain intermediate B. Under nitrogen protection, 800 ml of anhydrous tetrahydrofuran, 0.11 mol of 4-phosphono-2-(phosphonomethyl)-butyric acid, 0.25 mol of benzyl bromide, and 0.15 mol of potassium carbonate were mixed thoroughly and stirred at room temperature for 10 h. After filtration, 0.1 mol of intermediate B and 0.1 mol of 1-hydroxybenzotriazole were added and stirred thoroughly. Then, 0.11 mol of dicyclohexylcarbodiimide and 0.02 mol of... 4-Dimethylaminopyridine was reacted at 25°C for 18 h, filtered, and 1000 ml of cold anhydrous n-hexane was added to the filtrate and stirred to precipitate. The precipitate was filtered, and the filter cake was washed with cold anhydrous n-hexane (3 × 100 ml). 300 ml of tetrahydrofuran was added and stirred to dissolve the precipitate. 0.5 g of 10 wt% Pd / C was added, and the mixture was stirred at room temperature for 12 h under a hydrogen atmosphere (0.3 MPa). The mixture was filtered, and the filtrate was rotary evaporated at 45°C for 2 h and then dried under vacuum at 60°C for 12 h to obtain 2-{[(1-(hexylamino)tridecane-2-yl)oxy]carbonyl}butane-1,4-dimethylbisphosphonic acid.

[0032] The chemical structural formula of {[(1-(hexylamino)tetran-2-yl)oxy]carbonyl}butane-1,4-dimethylbisphosphonic acid is as follows: .

[0033] The raw material composition and preparation method of the unshaped refractory material in Comparative Example 4 are basically the same as those in Example 6, except that the binder is replaced with an equal weight of binder prepared by the following method: The preparation method of the binder is basically the same as that in Example 3, except that the ((3,13-diundecyl-2,14-dioxa-5,11-diazapentadecanoyl)bis(butane-2,1,4-triyl))tetraphosphonic acid in step S4 is replaced with (3,13-diundecyl-2,14-dioxa-5,11-diazapentadecanoyl)bis(butane-2,1,4-triyl))tetraphosphonic acid. Replace with an equimolar amount of ((3,13-dipropyl-2,14-dioxa-5,11-diazapentadecanediayl)bis(butane-1,2,4-triyl))tetraphosphonic acid; ((3,13-dipropyl-2,14-dioxa-5,11-diazapentadecanediayl)bis(butane-1,2,4-triyl))tetraphosphonic acid was prepared by the following method: N1: Under nitrogen protection, 250 ml of anhydrous acetonitrile, 0.1 mol 1,5-Diaminopentane and 0.205 mol of 1,2-epoxypentane were stirred and mixed, and the mixture was heated to 60 °C and reacted for 5 h. After cooling to room temperature, the mixture was distilled under reduced pressure at 50 °C for 1 h. 200 mL of cold anhydrous n-hexane was added and stirred to precipitate the solid. The solid was filtered, and the filter cake was washed with cold anhydrous n-hexane (3 × 50 mL). The solid was then dried under vacuum at 50 °C for 8 h to obtain intermediate C. Under nitrogen protection, 1000 mL of anhydrous tetrahydrofuran, 0.21 mol of 4-phosphono-2-(phosphonomethyl)-butyric acid, 0.5 mol of benzyl bromide, and 0.3 mol of potassium carbonate were mixed and stirred at room temperature for 10 h. After filtration, 0.1 mol of intermediate C and 0.1 mol of 1-hydroxybenzotriazole were added and stirred and mixed. 0.21 mol of dicyclohexylcarbodiimide and 0.04 mol of... 4-Dimethylaminopyridine was reacted at 25°C for 18 h, filtered, and 1200 ml of cold anhydrous n-hexane was added to the filtrate and stirred to precipitate. The precipitate was filtered, and the filter cake was washed with cold anhydrous n-hexane (3 × 120 ml). 400 ml of tetrahydrofuran was added and stirred to dissolve the precipitate. 0.5 g of 10 wt% Pd / C was added, and the mixture was stirred at room temperature for 12 h under a hydrogen atmosphere (0.3 MPa). The mixture was filtered, and the filtrate was rotary evaporated at 45°C for 2 h and then dried under vacuum at 60°C for 12 h to obtain ((3,13-dipropyl-2,14-dioxa-5,11-diazapentadecanoyl)bis(butane-1,2,4-triyl))tetraphosphonic acid.

[0034] The chemical structural formula of ((3,13-dipropyl-2,14-dioxa-5,11-diazapentadecanoyl)bis(butane-1,2,4-triyl))tetraphosphonic acid is as follows: .

[0035] The raw material composition and preparation method of the unshaped refractory material in Comparative Example 5 are basically the same as those in Example 6, except that the binder is replaced with an equal weight of binder prepared by the following method: The preparation method of the binder is basically the same as that in Example 3, except that the ((3,13-diundecyl-2,14-dioxa-5,11-diazapentadecanoyl)bis(butane-2,1,4-triyl))tetraphosphonic acid in step S4 is replaced with Replace with equimolar amounts of 4,18-dioxo-6,16-di(undecyl)-5,17-dioxa-8,14-diazateicoplano-1,21-diylbisphosphonic acid; 4,18-dioxo-6,16-di(undecyl)-5,17-dioxa-8,14-diazateicoplano-1,21-diylbisphosphonic acid was prepared by the following method: N1: Under nitrogen protection, 250 ml of anhydrous acetonitrile, 0.1 mol 1,5-Diaminopentane and 0.205 mol of 2-undecylethylene oxide were stirred and mixed, and the mixture was heated to 60 °C and reacted for 5 h. After cooling to room temperature, the mixture was distilled under reduced pressure at 50 °C for 1 h. 200 mL of cold anhydrous n-hexane was added and stirred to precipitate the solid. The solid was filtered, and the filter cake was washed with cold anhydrous n-hexane (3 × 50 mL). The solid was then dried under vacuum at 50 °C for 8 h to obtain intermediate A. Under nitrogen protection, 1000 mL of anhydrous tetrahydrofuran, 0.21 mol of 4-phosphonobutyric acid, 0.5 mol of benzyl bromide, and 0.3 mol of potassium carbonate were mixed and stirred at room temperature for 10 h. After filtration, 0.1 mol of intermediate A and 0.1 mol of 1-hydroxybenzotriazole were added and stirred until well mixed. 0.21 mol of dicyclohexylcarbodiimide and 0.04 mol of... 4-Dimethylaminopyridine was reacted at 25°C for 18 h, filtered, and 1200 ml of cold anhydrous n-hexane was added to the filtrate and stirred to precipitate. The precipitate was filtered, and the filter cake was washed with cold anhydrous n-hexane (3 × 120 ml). 400 ml of tetrahydrofuran was added and stirred to dissolve the precipitate. 0.5 g of 10 wt% Pd / C was added, and the mixture was stirred at room temperature for 12 h under a hydrogen atmosphere (0.3 MPa). The mixture was filtered, and the filtrate was rotary evaporated at 45°C for 2 h and then dried under vacuum at 60°C for 12 h to obtain 4,18-dioxo-6,16-di(undecyl)-5,17-dioxa-8,14-diazatecosane-1,21-diylbisphosphonic acid.

[0036] The chemical structural formula of 4,18-dioxo-6,16-di(undecyl)-5,17-dioxa-8,14-diazacotetradecane-1,21-diylbisphosphonic acid is as follows: .

[0037] The magnesium aluminum spinel used in the embodiments and comparative examples of this application is model MA-65, produced by Sanmenxia Shuntai Fused Corundum Co., Ltd.; the silica has a particle size uniformly distributed between 2-5 mm, and its composition is as follows: 98.83% SiO2, 0.17% Al2O3, 0.7% Fe2O3, 0.05% CaO, 0.01% MgO, 0.05% K2O, 0.01% Na2O, 0.01% TiO2; the SiO2 powder has a particle size uniformly distributed between 20-25 μm; the fly ash is Class I fly ash, with a particle size uniformly distributed between 1-40 μm, and its composition is as follows: 58.47% SiO2, 19.04% Al2O3, 10.92% CaO, 5.78% MgO, 0.97% Fe2O3; the polycarboxylate high-performance water-reducing agent is model SPC-100, produced by Liaoning Kelong Fine Chemical Co., Ltd.; the CAS number of 4-phosphono-2-(phosphonomethyl)-butyric acid is 51360-27-1.

[0038] The mechanical properties, slag resistance, and thermal shock resistance of the unshaped refractory materials prepared in Examples 5-7 and Comparative Examples 1-5 were tested. The test results are shown in Table 1.

[0039] Mechanical property testing: Sample preparation was carried out in accordance with Section 5.1 of GB / T 4513.5-2017: The unshaped refractory materials prepared in Examples 5-7 and Comparative Examples 1-5 were placed in a polytetrafluoroethylene mold with dimensions of 160mm×40mm×40mm. The molding method was vibration molding with an amplitude of 0.5mm. After vibration for 5 minutes, the sample was obtained. The sample was placed in the mold and cured at 20℃ for 10 hours. After curing, it was immediately placed in a drying oven at 110℃ for 18 hours and allowed to cool naturally to room temperature. Then, the room temperature flexural strength was tested in accordance with GB / T 3001-2017 "Test Method for Flexural Strength of Refractory Materials at Room Temperature" with a loading rate of 0.15MPa / s.

[0040] Slag resistance test: Samples were prepared according to YB / T 5202.1-2003 standard: The unshaped refractory materials prepared in Examples 5-7 and Comparative Examples 1-5 were placed in a polytetrafluoroethylene mold with dimensions of 70mm×70mm×65mm. The molding method was vibration molding with an amplitude of 0.5mm. After vibration for 90s, the sample was obtained. The sample with the mold was placed in an oven at 110℃ and dried for 12h. After demolding, it was dried again under the same conditions for 24h and naturally cooled to room temperature. A crucible sample with an inner diameter of 40mm and a depth of 30mm was drilled from the center of the top surface of the sample. The slag resistance test was carried out according to the static crucible method in standard GB / T 8931-2007 "Test Method for Slag Resistance of Refractory Materials".

[0041] Thermal shock resistance test: Samples were prepared according to YB / T 5202.1-2003 standard. The unshaped refractory materials prepared in Examples 5-7 and Comparative Examples 1-5 were placed in a polytetrafluoroethylene mold with dimensions of 230mm × 114mm × 65mm. The molding method was vibration molding with an amplitude of 0.5mm. After vibration for 90s, the samples were obtained. The samples, still in the mold, were dried in an oven at 110℃ for 12h. After demolding, they were dried again under the same conditions for 24h and then naturally cooled to room temperature. The thermal shock resistance test was conducted using the air quenching method in standard GB / T 30873-2014 "Test Method for Thermal Shock Resistance of Refractory Materials". The initial flexural strength (strength before thermal shock) and the flexural strength after complete cooling (strength after thermal shock) of the samples were measured. The strength retention rate was calculated using the formula: Strength retention rate = Strength after thermal shock / Strength before thermal shock × 100%, which was used to evaluate the thermal shock stability of the samples.

[0042] Table 1 Performance Test Data

[0043] As can be seen from the data in Table 1, the unshaped refractory materials prepared in Examples 5-7 of this application possess excellent mechanical properties, slag resistance, and thermal shock resistance. This is because the binders added to the components have phosphonate, siloxane segments, borate esters, long-chain alkyl groups, and furan ring structures, exhibiting a significant synergistic reinforcing effect in the unshaped refractory material system. Among these, the long-chain alkyl groups provide certain hydrophobicity and lubricity, which is beneficial for the uniform dispersion of the refractory material and improves the compact packing of particles in the early stages of forming; the phosphonate groups, through chelation, bind with the Mg on the surface of the magnesium aluminate spinel aggregate. 2+ Al 3+ Stable coordination bonds are formed between the active metal ions in fly ash and the siloxane chains and the hydroxyl groups on the surface of SiO2 micropowder, constructing a chelate-covalent double network structure, which significantly improves the strength at room temperature. At high temperature, the furan ring forms a residual carbon network through aromatic condensation, and the B2O3 generated by the borate ester promotes medium-temperature sintering. The two work synergistically to fill the strength trough caused by the decomposition of the organic binder. After the siloxane decomposes at high temperature, it generates active SiO2, which reacts with Al2O3 and MgO in the system to form a ceramic phase, forming a high-temperature strength support, thereby improving the mechanical properties of the monolithic refractories. In addition, the phosphonate chelate layer forms a chemical barrier at the aggregate-slag interface, inhibiting Ca2+. 2+ Fe 3 +Plasma penetration and erosion; the siloxane-derived -Si-O-Si- network exhibits excellent chemical stability, reducing the wettability of the matrix by molten slag; the furan ring structure undergoes cross-linking and carbonization during heating to form an aromatic carbon skeleton, strengthening the initial strength of the material and further improving its slag resistance, thus delaying slag penetration and material erosion. The composite structure of furan ring residual carbon and ceramic phase forms a matrix that combines rigidity and flexibility, reducing the material's coefficient of thermal expansion; the low-melting-point glass phase generated by the decomposition of borate esters can fill microcracks during thermal cycling, inhibiting crack propagation and thereby improving the material's thermal shock resistance. In Comparative Example 3, the binder molecule contained only one phosphonate, siloxane segment, borate ester, long-chain alkyl group, and furan ring structure, resulting in a decrease in the mechanical properties, slag resistance, and thermal shock resistance of the prepared monolithic refractory material compared to the examples.

[0044] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. However, any modifications, alterations, and variations made by those skilled in the art without departing from the scope of the present invention based on the disclosed technical content are equivalent embodiments of the present invention. Furthermore, any modifications, alterations, and variations made to the above embodiments based on the essential technology of the present invention are still within the protection scope of the present invention.

Claims

1. An unshaped refractory material, characterized in that, The raw materials include the following parts by weight: 60-80 parts of refractory aggregate, 25-35 parts of powder, 8-10 parts of binder, and 0.5-1 parts of water-reducing agent; the binder is prepared by the following method: S1: glycidyl methacrylate reacts with furanoic acid to generate intermediate 1, S2: intermediate 1 reacts with 3-glycidyl etheroxypropyltriethoxysilane to generate intermediate 2, S3: intermediate 2 reacts with pinacol 4-chloromethylphenylboronic acid to generate intermediate 3, S4: intermediate 3 reacts with ((3,13-diundecyl-2,14-dioxa-5,11-diazapentadecanoyl)bis(butane-2,1,4-triyl))tetraphosphonic acid to generate the binder.

2. The unshaped refractory material according to claim 1, characterized in that, In step S1, the molar ratio of glycidyl methacrylate to furanoic acid is 1:(1.05-1.1).

3. The unshaped refractory material according to claim 1, characterized in that, In step S2, the molar ratio of intermediate 1 to 3-glycidyl etheroxypropyltriethoxysilane is 1:(1.05-1.1).

4. The unshaped refractory material according to claim 1, characterized in that, In step S3, the molar ratio of intermediate 2 to pinacol 4-chloromethylphenylboronic acid is 1:(1.1-1.2).

5. The unshaped refractory material according to claim 1, characterized in that, In step S4, the molar ratio of intermediate 3 to ((3,13-diundecyl-2,14-dioxa-5,11-diazapentadecanoyl)bis(butane-2,1,4-triyl))tetraphosphonic acid is (2.1-2.2):

1.

6. The unshaped refractory material according to claim 1, characterized in that, The refractory aggregate includes magnesium aluminum spinel and silica, wherein the magnesium aluminum spinel accounts for 60% by weight and the silica accounts for 40% by weight.

7. The unshaped refractory material according to claim 1, characterized in that, The powder includes SiO2 micro powder and fly ash, wherein the weight percentage of SiO2 micro powder is 40% and the weight percentage of fly ash is 60%.

8. The unshaped refractory material according to claim 1, characterized in that, The water-reducing agent is a polycarboxylate high-performance water-reducing agent.

9. A method for preparing the unshaped refractory material according to any one of claims 1-8, characterized in that, The steps include: (1) Weighing by weight: 60-80 parts of refractory aggregate, 25-35 parts of powder, 8-10 parts of binder, and 0.5-1 parts of water-reducing agent; (2) Drying the refractory aggregate and powder to obtain pretreated refractory aggregate and powder; The pretreated refractory aggregate, powder, binder, and water-reducing agent are mixed evenly to obtain unshaped refractory material.

10. The application of an unshaped refractory material as described in any one of claims 1-8 in an industrial kiln.

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