Preparation method of high-wear-resistance thermosetting polyurethane modified by anilino trapezoidal polysilsesquioxane

Abstract

The preparation method comprises the following steps: adding phenyl trapezoidal polysilsesquioxane into fuming nitric acid, stirring at a low temperature for 0.5 h, then stirring at room temperature for 5-20 h, precipitating with ice water, drying, dissolving in tetrahydrofuran and triethylamine, adding a palladium-carbon catalyst, stirring at the room temperature for 5-20 h, then adding a catalyst, stirring at the room temperature for 5-20 h, and finally adding a catalyst to obtain the high-wear-resistance thermosetting polyurethane modified by the phenyl trapezoidal polysilsesquioxane, thereby obtaining the high-wear-resistance thermosetting polyurethane modified by the phenyl trapezoidal polysilsesquioxane. Slowly adding formic acid at 50-80 DEG C to react for 1-5 hours, filtering the suspension, washing and drying to obtain anilino trapezoidal polysilsesquioxane; the preparation method comprises the following steps: uniformly mixing polyol, diisocyanate and a first catalyst, heating to 60-110 DEG C, and reacting for 1-3 hours to obtain a polyurethane prepolymer; and adding anilino trapezoidal polysilsesquioxane into the polyurethane prepolymer, reacting for 0.5-5 hours at the temperature of 25-60 DEG C, and demolding to obtain the high-wear-resistance thermosetting polyurethane. Compared with traditional polyurethane, the obtained high-wear-resistance thermosetting polyurethane has the advantages of excellent high wear resistance, excellent mechanical properties and the like, and can be applied to a lining of a grinding machine.

Description

Technical Field

[0001] The present invention relates to the field of highly wear-resistant polyurethane materials, in particular to a highly wear-resistant thermosetting polyurethane and a synthesis method thereof. Background Art

[0002] Polyurethane materials have excellent mechanical, chemical resistance, wear resistance and other properties, and are widely used in the fields of automobiles, machinery, electronics, aerospace, etc. Although polyurethane materials have many advantages, with the development of society and the progress of industry, the improvement of the performance of polyurethane materials is particularly important. For equipment under special working conditions such as mine magnetic separators, flotation machines, belt conveyor rollers, coal mine conveyor belts, etc., due to the very harsh use environment, these mechanical equipment and conveying equipment are severely worn during use, seriously affecting their service life. The demand for highly wear-resistant polyurethane materials is becoming more and more urgent.

[0003] The core of phenyl ladder polysilsesquioxane is a ladder-shaped structure composed of silica ladder chains side by side. The phenyl group is located on the side of the ladder structure, and the ladder end group is connected to the hydroxyl group. Its spatial structural dimension is higher than that of ordinary branched structure polysiloxane. The polymer can be modified by physical blending or chemical copolymerization to provide a larger spatial structure for the cross-linked network of the cured material, thereby improving the mechanical properties and thermal stability of the material. The benzene ring and silica ladder chain give the structure excellent mechanical properties, high temperature stability, durability and weather resistance.

[0004] The invention discloses a preparation method of a highly wear-resistant thermosetting polyurethane modified by aniline ladder polysilsesquioxane, wherein phenyl ladder polysilsesquioxane is added to fuming nitric acid and stirred at low temperature for 0.5h, then stirred at room temperature for 5-20h, precipitated with ice water, dried, dissolved in tetrahydrofuran and triethylamine, and then a palladium carbon catalyst is added, formic acid is slowly added at 50-80°C for reaction for 1-5h, the suspension is filtered, washed and dried to obtain aniline ladder polysilsesquioxane; polyol, diisocyanate and the first catalyst are mixed and heated to 60-110°C for reaction for 1-3h to obtain a polyurethane prepolymer; aniline ladder polysilsesquioxane is added to the above polyurethane prepolymer, reacted at 25-60°C for 0.5h-5h, and highly wear-resistant thermosetting polyurethane is obtained after demoulding. The highly wear-resistant thermosetting polyurethane obtained by the invention has the advantages of excellent high wear resistance, mechanical properties and the like compared with traditional polyurethane. Summary of the invention

[0005] The purpose of the present invention is to provide a method for preparing a highly wear-resistant thermosetting polyurethane modified by aniline-based ladder-shaped polysilsesquioxane.

[0006] In order to achieve the above objectives, the following technical solutions are provided:

[0007] A method for preparing a highly wear-resistant thermosetting polyurethane modified by an aniline-based ladder-shaped polysilsesquioxane comprises the following steps:

[0008] (1) 1 mol of phenyl ladder polysilsesquioxane is added to fuming nitric acid and stirred at low temperature for 0.5 h, then stirred at room temperature for 5-20 h, precipitated with ice water, dried, dissolved in tetrahydrofuran and triethylamine, and then 0.01-0.1 mol of palladium carbon catalyst is added, 2-4 mol of formic acid is slowly added at 50-80° C. and reacted for 1-5 h, the suspension is filtered, washed and dried to obtain aniline ladder polysilsesquioxane.

[0009] (2) 1 to 2 moles of polyol, 1 to 2 moles of diisocyanate and 0.05 to 0.1 moles of a first catalyst are mixed, and the mixture is heated to 60 to 110° C. and reacted for 1 to 3 hours to obtain a polyurethane prepolymer solution.

[0010] (3) Add the product of (1) to the above-mentioned polyurethane prepolymer and mix well, press into a mold, react at 25-60° C. for 0.5 h to 5 h, and obtain a highly wear-resistant thermosetting polyurethane after demolding.

[0011] Preferably, the method for preparing the highly wear-resistant thermosetting polyurethane modified with aniline-based trapezoidal polysilsesquioxane is characterized in that the polyol is polytetramethylene glycol, polypropylene oxide glycol, polyester glycol, etc., but is not limited thereto.

[0012] Preferably, the method for preparing the highly wear-resistant thermosetting polyurethane modified with aniline-based trapezoidal polysilsesquioxane is characterized in that the diisocyanate is toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, etc., but is not limited thereto.

[0013] Preferably, the method for preparing the highly wear-resistant thermosetting polyurethane modified with aniline-based trapezoidal polysilsesquioxane is characterized in that the first catalyst is dibutyltin dilaurate, stannous octoate, etc., but is not limited thereto.

[0014] The beneficial effect of the present invention is that the thermosetting polyurethane is generated by reacting the aniline-based ladder-shaped polysilsesquioxane having both rigidity and flexibility, high wear resistance and mechanical properties with a polyol and a diisocyanate to generate a polyurethane prepolymer. The wear resistance and mechanical properties of the thermosetting polyurethane are significantly improved compared with traditional polyurethane products. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 The invention is a method for preparing a highly wear-resistant thermosetting polyurethane modified with an aniline-based ladder-shaped polysilsesquioxane, and the hydrogen nuclear magnetic resonance spectrum of the product of (1) in Example 1; Specific implementation methods

[0017] The principle of the invention is that polyol and diisocyanate react to form prepolymer, which then reacts with chain extender aniline ladder polysilsesquioxane to obtain polyurethane. The rigid and flexible properties of aniline ladder polysilsesquioxane are used to improve various properties of polyurethane.

[0018] The present invention will be further described below with reference to the accompanying drawings and embodiments, and the purpose and effects of the present invention will become more apparent.

[0019] Embodiment 1:

[0020] (1) 1 mol of phenyl ladder polysilsesquioxane is added to 200 mL of fuming nitric acid and stirred at low temperature for 0.5 h, and then stirred at room temperature for 20 h. After the reaction is completed, 500 g of ice water is used for precipitation, and after drying, it is dissolved in 250 mL of tetrahydrofuran and 250 mL of triethylamine, and then 0.1 mol of palladium carbon catalyst is added, and 1 mol of formic acid is slowly added at 50° C. After reacting for 5 h, the suspension is filtered, washed, and dried to obtain aniline ladder polysilsesquioxane.

[0021] (2) 1 mol of polytetrahydrofuran diol, 1 mol of toluene diisocyanate and 0.05 mol of dibutyltin dilaurate are heated to 110° C. and reacted for 1 hour to obtain a polyurethane prepolymer.

[0022] (3) Add the product of (1) to the above-mentioned polyurethane prepolymer and mix well, press into a mold, react at 60° C. for 0.5 h, and obtain a highly wear-resistant thermosetting polyurethane after demolding.

[0023] Embodiment 2:

[0024] (1) 1 mol of phenyl ladder polysilsesquioxane is added to 200 mL of fuming nitric acid and stirred at low temperature for 0.5 h, and then stirred at room temperature for 20 h. After the reaction is completed, 500 g of ice water is used for precipitation, and after drying, it is dissolved in 250 mL of tetrahydrofuran and 250 mL of triethylamine, and then 0.1 mol of palladium carbon catalyst is added, and 1 mol of formic acid is slowly added at 80° C. After reacting for 1 h, the suspension is filtered, washed, and dried to obtain aniline ladder polysilsesquioxane.

[0025] (2) 1 mol of polytetrahydrofuran diol, 1 mol of diphenylmethane diisocyanate and 0.1 mol of dibutyltin dilaurate were mixed and then heated to 60° C. for reaction for 3 h to obtain a polyurethane prepolymer.

[0026] (3) Add the product of (1) to the above-mentioned polyurethane prepolymer and mix well, press into a mold, react at 25° C. for 5 hours, and obtain a highly wear-resistant thermosetting polyurethane after demolding.

[0027] Embodiment 3:

[0028] (1) 1 mol of phenyl ladder polysilsesquioxane is added to 200 mL of fuming nitric acid and stirred at low temperature for 0.5 h, and then stirred at room temperature for 20 h. After the reaction is completed, 500 g of ice water is used for precipitation, and after drying, it is dissolved in 250 mL of tetrahydrofuran and 250 mL of triethylamine, and then 0.1 mol of palladium carbon catalyst is added, and 1 mol of formic acid is slowly added at 50° C. After reacting for 5 h, the suspension is filtered, washed, and dried to obtain aniline ladder polysilsesquioxane.

[0029] (2) 1 mol of polytetrahydrofuran diol and 1 mol of hexamethylene diisocyanate are added with 0.05 mol of dibutyltin dilaurate and the mixture is heated to 110° C. and reacted for 1 hour to obtain a polyurethane prepolymer.

[0030] (3) Add the product of (1) to the above-mentioned polyurethane prepolymer and mix well, press into a mold, react at 60° C. for 0.5 h, and obtain a highly wear-resistant thermosetting polyurethane after demolding.

[0031] Embodiment 4:

[0032] (1) 1 mol of phenyl ladder polysilsesquioxane is added to 200 mL of fuming nitric acid and stirred at low temperature for 0.5 h, and then stirred at room temperature for 20 h. After the reaction is completed, 500 g of ice water is used for precipitation, and after drying, it is dissolved in 250 mL of tetrahydrofuran and 250 mL of triethylamine, and then 0.1 mol of palladium carbon catalyst is added, and 1 mol of formic acid is slowly added at 50° C. After reacting for 5 h, the suspension is filtered, washed, and dried to obtain aniline ladder polysilsesquioxane.

[0033] (2) 1 mol of polypropylene oxide diol, 1 mol of toluene diisocyanate and 0.1 mol of dibutyltin dilaurate were mixed and then heated to 60° C. for reaction for 3 h to obtain a polyurethane prepolymer.

[0034] (3) Add the product of (1) to the above-mentioned polyurethane prepolymer and mix well, press into a mold, react at 60° C. for 0.5 h, and obtain a highly wear-resistant thermosetting polyurethane after demolding.

[0035] Embodiment 5:

[0036] (1) 1 mol of phenyl ladder polysilsesquioxane is added to 200 mL of fuming nitric acid and stirred at low temperature for 0.5 h, and then stirred at room temperature for 20 h. After the reaction is completed, 500 g of ice water is used for precipitation, and after drying, it is dissolved in 250 mL of tetrahydrofuran and 250 mL of triethylamine, and then 0.1 mol of palladium carbon catalyst is added, and 1 mol of formic acid is slowly added at 50° C. After reacting for 5 h, the suspension is filtered, washed, and dried to obtain aniline ladder polysilsesquioxane.

[0037] (2) 1 mol of polyoxypropylene diol and 1 mol of diphenylmethane diisocyanate are added with 0.05 mol of dibutyltin dilaurate and the mixture is heated to 110° C. and reacted for 1 hour to obtain a polyurethane prepolymer.

[0038] (3) Add the product of (1) to the above-mentioned polyurethane prepolymer and mix well, press into a mold, react at 25° C. for 5 hours, and obtain a highly wear-resistant thermosetting polyurethane after demolding.

[0039] Embodiment 6:

[0040] (1) 1 mol of phenyl ladder polysilsesquioxane is added to 200 mL of fuming nitric acid and stirred at low temperature for 0.5 h, and then stirred at room temperature for 20 h. After the reaction is completed, 500 g of ice water is used for precipitation, and after drying, it is dissolved in 250 mL of tetrahydrofuran and 250 mL of triethylamine, and then 0.1 mol of palladium carbon catalyst is added, and 1 mol of formic acid is slowly added at 80° C. After reacting for 1 h, the suspension is filtered, washed, and dried to obtain aniline ladder polysilsesquioxane.

[0041] (2) 1 mol of polypropylene oxide diol and 1 mol of hexamethylene diisocyanate are added with 0.05 mol of dibutyltin dilaurate and the mixture is heated to 60° C. and reacted for 3 h to obtain a polyurethane prepolymer.

[0042] (3) Add the product of (1) to the above-mentioned polyurethane prepolymer and mix well, press into a mold, react at 60° C. for 0.5 h, and then demold to obtain a highly wear-resistant thermosetting polyurethane.

[0043] Table 1: Hardness and wear resistance test of polyurethane

[0044] Example Shore A hardness <![CDATA[Akron Wear / mm 3 > Example 1 93 10 Example 2 90 11 Example 3 92 11 Example 4 90 12 Example 5 92 10 Example 6 94 11

Claims

1. A method for preparing a highly wear-resistant thermosetting polyurethane modified with aniline-based ladder-shaped polysilsesquioxane, characterized in that: The following steps are involved: (1) adding 1 mole of phenyl ladder polysilsesquioxane to fuming nitric acid and stirring at low temperature for 0.5 h, then stirring at room temperature for 5-20 h, precipitating with ice water, drying, dissolving in tetrahydrofuran and triethylamine, adding 0.01-0.1 mole of palladium carbon catalyst, slowly adding 2-4 moles of formic acid at 50-80° C. and reacting for 1-5 h, filtering the suspension, washing and drying to obtain aniline ladder polysilsesquioxane; (2) mixing 1 to 2 moles of polyol, 1 to 2 moles of diisocyanate and 0.05 to 0.1 moles of a first catalyst, heating the mixture to 60 to 110° C. and reacting the mixture for 1 to 3 hours to obtain a polyurethane prepolymer solution; (3) Add the product of (1) to the above-mentioned polyurethane prepolymer and mix well, press into a mold, react at 25-60° C. for 0.5 h to 5 h, and obtain a highly wear-resistant thermosetting polyurethane after demolding.

2. The method for preparing a highly wear-resistant thermosetting polyurethane modified with aniline-based ladder-shaped polysilsesquioxane according to claim 1, characterized in that: The polyols are polytetrahydrofuran diol, polypropylene oxide diol, polyester diol and the like.

3. The method for preparing a highly wear-resistant thermosetting polyurethane modified with aniline-based ladder-shaped polysilsesquioxane according to claim 1, characterized in that: The diisocyanate is toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and the like.

4. The method for preparing a highly wear-resistant thermosetting polyurethane modified with aniline-based ladder-shaped polysilsesquioxane according to claim 1, characterized in that: The first catalyst is dibutyltin dilaurate, stannous octoate, etc.

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