Imidazolium polyester polyol and polyurethane synthesized therefrom and preparation method thereof

Abstract

The invention discloses an imidazolium polyester polyol and a polyurethane synthesized therefrom and a preparation method thereof, belonging to the technical field of polyurethane foam. The imidazolium polyester polyol comprises the following raw materials: imidazolium bromide diol and imidazolium sulfonate dibasic acid, wherein the molar ratio of imidazolium sulfonate dibasic acid to imidazolium bromide diol is 1 moL:(1.05-1.55) moL; wherein the raw materials of imidazolium bromide diol comprise N-imidazole compounds and dibromodiol substances in a molar ratio of (2.01-2.1) moL:1 moL, the raw materials of imidazolium sulfonate dibasic acid comprise dibasic acid grafted with imidazole groups and 1,3-propane sultone in a molar ratio of 1 moL:1 moL, and the dibasic acid grafted with imidazole groups comprises 1,3,5-pentanetricarboxylic acid and imidazole alcohol substances in a molar ratio of 1 moL:1 moL. The polyester polyol synthesized by the imidazolium polyester polyol is used for the synthesis of polyurethane foam, has antibacterial and antiviral effects, and has good mechanical properties, thermal properties and chemical resistance.

Description

Technical Field

[0001] The invention relates to the technical field of polyurethane foam, in particular to an imidazolium polyester polyol and a polyurethane synthesized therefrom and a preparation method thereof. Background Art

[0002] As an important synthetic polymer material, polyurethane foam is widely used in many fields due to its excellent properties such as high flexibility, shape memory and easy functionalization. In order to meet the needs of industries such as healthcare, textile materials and food packaging for antibacterial and antiviral properties, researchers are committed to developing polyurethane foam with antibacterial and antiviral functions. At present, there are four main functionalization methods to give polyurethane antibacterial and antiviral properties: 1. Physical blending method, that is, directly mixing antibacterial and antiviral raw materials into polyurethane, which is easy to operate but may cause the original performance of polyurethane to decline, and the antibacterial and antiviral properties are easily attenuated due to the loss of additives during long-term use. 2. Functionalized isocyanate method, polyurethane is prepared by synthesizing polyisocyanates with antibacterial and antiviral groups. However, this method has problems such as high difficulty in synthesis and low reactivity of functionalized isocyanates, which may lead to poor comprehensive performance of the final polyurethane product. 3. Antibacterial and antiviral additive cross-linking method, adding antibacterial and antiviral additives during the synthesis of polyurethane. This method is limited by the limited number of groups that the additives can access on the polyurethane chain, and the antibacterial and antiviral effects may not be ideal. 4. The functionalized polyol method connects antibacterial and antiviral active substances to the polyurethane chain through chemical bonds. This method can maintain the antibacterial and antiviral effects for a long time, but the current challenge is mainly that the cost of functional polyols is relatively high and is not suitable for large-scale commercial production.

[0003] Studies have found that imidazole groups and their derivatives such as imidazolium ions have good thermal stability and efficient antibacterial and antiviral properties, especially showing a positive effect on inhibiting fungal growth and destroying viral protein structures. However, when imidazole groups or imidazolium ions are directly introduced into the main chain of polyurethane, the mechanical properties, thermal stability and biodegradability of polyurethane may be affected, thereby limiting its application in actual industrial production. In addition, in the reaction of synthesizing bromine-containing imidazolium ion diols, nitrogen is often used as a protective gas. Although nitrogen, as an inert gas, can effectively block the side reactions caused by oxygen, it cannot act on the hyperconjugated structure formed between the bromine group and the hydroxyl group, which is not conducive to the formation of bromine-containing imidazolium diols. Summary of the invention

[0004] The invention aims to provide an imidazolium polyester polyol and a polyurethane synthesized therefrom and a preparation method thereof. A dibasic acid of imidazolium ions containing sulfonic acid groups (hereinafter referred to as imidazolium sulfonic acid dibasic acid) is reacted with a diol of imidazolium ions containing bromine (hereinafter referred to as imidazolium bromine diol) to obtain a polyester polyol containing imidazolium side chains (hereinafter referred to as imidazolium polyester polyol), which is used for the synthesis of polyurethane foam. The obtained polyurethane foam contains multiple imidazolium structures on the side chains, can play an antibacterial and antiviral role, and has good mechanical properties, thermal properties and chemical resistance. The production cost is lower than that of conventional antibacterial and antiviral polyurethanes.

[0005] The invention provides an imidazolium polyester polyol, comprising the following raw materials: imidazolium bromide diol and imidazolium sulfonate dibasic acid, wherein the molar ratio of imidazolium sulfonate dibasic acid to imidazolium bromide diol is 1 moL:(1.05-1.55) moL; wherein the raw materials of imidazolium bromide diol comprise N-imidazole compounds and dibromodiol substances in a molar ratio of (2.01-2.1) moL:1 moL, the raw materials of imidazolium sulfonate dibasic acid comprise dibasic acid grafted with imidazole groups and 1,3-propanesulfone in a molar ratio of 1 moL:1 moL, and the dibasic acid grafted with imidazole groups comprises 1,3,5-pentanetricarboxylic acid and imidazole alcohol substances in a molar ratio of 1 moL:1 moL.

[0006] The present invention provides a method for preparing an imidazolium polyester polyol, comprising the following steps:

[0007] S1, mixing an N-imidazole compound with a dibromodiol substance, adding a solvent, reacting in a protective gas atmosphere, and then removing impurities by rotary evaporation to obtain imidazolium bromodiol;

[0008] S2, using 1,3,5-pentanetricarboxylic acid to react with an imidazole alcohol substance to form a dibasic acid grafted with an imidazole group;

[0009] S3, reacting the dibasic acid grafted with imidazole groups obtained in S2 with 1,3-propane sultone, and then removing impurities by rotary evaporation to obtain imidazole onium sulfonate dibasic acid;

[0010] S4, polycondensing the imidazolium sulfonate dibasic acid obtained in S3 with the imidazolium bromide diol obtained in S1 to obtain imidazolium polyester polyol.

[0011] Preferably, in step S1, the N-imidazole compound is one or more of N-methylimidazole, N-ethylimidazole, N-n-propylimidazole, N-isopropylimidazole, N-n-butylimidazole, N-tert-butylimidazole, and N-phenylimidazole; the dibromodiol substance is one or more of 2,3-dibromo-1,4-butanediol, 2,2-dibromo-1,4-butanediol, 2,2-dibromo-1,5-pentanediol, dibromoneopentyl glycol, 3,6-dibromophenanthrene-9,10-diol, and 1,8-dibromo-2,7-dihydroxynaphthalene; the solvent is one or more of tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, 1,3-dioxolane, and 1,4-dioxane; and the protective gas for the reaction of the N-imidazole substance with the dibromodiol substance is one or more of CO2 or N2.

[0012] Preferably, in step S2, the imidazole alcohol substance added is one or more of 1-hydroxymethylimidazole, 1-(2-hydroxyethyl)imidazole, 1-(3-hydroxypropyl)-1H-imidazole, 2-(1H-imidazol-1-yl)propane-1-ol, 1-(2-hydroxypropyl)imidazole, and 2-(2-methyl-1H-imidazol-1-yl)ethanol.

[0013] Preferably, in step S3, the molar ratio of the dibasic acid grafted with imidazole groups to 1,3-propane sultone is 1 mol:1 mol.

[0014] Preferably, the specific steps of step S4 are: adding the imidazolium sulfonate dibasic acid obtained in S3 and the imidazolium bromine diol obtained in S1 to a reactor, reacting under nitrogen protection, adding a metal catalyst, stopping the nitrogen flow, turning on a vacuum pump to evacuate, reacting after heating, and cooling to room temperature when the acid value of the reaction product is ≤1.0 mgKOH / g to obtain an imidazolium polyester polyol; the metal catalyst is a catalyst commonly used in the synthesis of polyester polyols, which is one of dibutyltin dilaurate, stannous octoate, isopropyl titanate, tetrabutyl titanate, antimony trioxide, and zinc acetate, and the amount used is 0.05-1.5% of the total reactant mass.

[0015] Preferably, in step S1, the reaction temperature of N-imidazole substances and dibromodiol substances is 60-90°C, and the reaction time is 5-24h; in S2, the reaction temperature of 1,3,5-pentanetricarboxylic acid and imidazole alcohol substances is 140-180°C, and the reaction time is 1-8h; in S3, the reaction temperature of the dibasic acid grafted with imidazole groups and 1,3-propanesultone is 60-90°C, and the reaction time is 5-24h; in S4, the reaction temperature of imidazolesulfonate dibasic acid and imidazolebromide diol under nitrogen protection is 140-180°C, and the reaction time is 4-10h; the vacuum degree of the reaction of imidazolesulfonate dibasic acid and imidazolebromide diol under vacuum environment is 0.75-0.95bar, the reaction temperature is 190-220°C, and the reaction time is 1-6h.

[0016] The invention provides a polyurethane synthesized from imidazolium polyester polyol. The polyurethane comprises the following raw materials: imidazolium polyester polyol and polyethylene adipate polyol / polyether polyol in a mass ratio of 1:(5-105), a chain extender added in an amount of 2-5 parts per 100 parts of the polyol, a foam stabilizer added in an amount of 2-5 parts per 100 parts of the polyol, a catalyst added in an amount of 0.5-1.5 parts per 100 parts of the polyol, a foaming agent added in an amount of 2-5 parts per 100 parts of the polyol, and an isocyanate substance added in an amount of 50-100 parts per 100 parts of the polyol.

[0017] The invention provides a preparation method of polyurethane synthesized from polyester polyol synthesized from imidazolium polyester polyol. The obtained imidazolium polyester polyol is mixed with polyethylene adipate polyol / polyether polyol, and then mixed with a chain extender, a foam stabilizer, a catalyst and a foaming agent, and the mixed material is recorded as material A; an isocyanate substance is added into a container, which is recorded as material B; the material B is poured into a reactor filled with the material A, stirred at room temperature, poured into a mold for free foaming, and put into an oven for ripening after the foam surface is no longer sticky.

[0018] Preferably, the molecular weight of the imidazolium polyester polyol is 500-10000 and the hydroxyl value is 11 mgKOH / g -220mg KOH / g The molar ratio of imidazolium polyester polyol to polyethylene adipate polyol / polyether polyol is 1 moL:(10-1000) moL, the chain extender is one of ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, and 1,5-pentanediol; the foam stabilizer is silicone oil M-8860; the catalyst is one of dibutyltin dilaurate, diethanolamine, triethanolamine, N-ethylmorpholine, N-methylmorpholine, and A-33; the isocyanate substance is one of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate.

[0019] Therefore, the present invention adopts the above-mentioned imidazolium polyester polyol and the synthesized polyurethane and the preparation method thereof. The polyurethane foam containing imidazolium ions has good antibacterial and antiviral properties. The prepared polyurethane shows good inhibitory effects on Escherichia coli and Staphylococcus aureus, and shows good inactivation effects on the spike glycoprotein in the coronavirus, and the antibacterial and antiviral properties do not decrease with time. The imidazolium ion structure is introduced into the side chain. Imidazole has an aromatic structure. Compared with the quaternary ammonium salt group, it has higher thermal stability and can enhance the spatial structure of the molecule. The synthesized polyurethane has good mechanical properties, thermal properties and chemical resistance. In the reaction of N-imidazole substances with dibromodiol substances, CO is used. 2 The protective gas can promote the nucleophilic substitution reaction of the imidazole group, weaken the hyperconjugation effect between the bromine group and the hydroxyl group in the dibromodiol substances, accelerate the reaction rate and shorten the reaction time.

[0020] The technical solution of the present invention is further described in detail below through the accompanying drawings and embodiments. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] In the figure below, 2NIM-PU represents polyurethane grafted with imidazolium bromide and imidazole sulfonic acid structures, 1NIM-PU represents polyurethane grafted with imidazolium bromide structure, IM-PU represents polyurethane grafted with only imidazole groups, and PU represents polyurethane without grafted structure; NIM-PU represents polyurethane containing imidazolium structure, and PU represents polyurethane without imidazolium structure;

[0022] Figure 1 The thermogravimetric analysis curves of polyurethane containing imidazolium structure and polyurethane without imidazolium structure, wherein (a) is polyurethane containing imidazolium structure; (b) is polyurethane without imidazolium structure;

[0023] Figure 2 This is a graph showing the effect of imidazolium structure on the chemical resistance of polyurethane materials;

[0024] Figure 3 This is a graph showing the relationship between the residual viral activity of polyurethane foam and time. DETAILED DESCRIPTION

[0025] The technical solution of the present invention is further described below through the accompanying drawings and embodiments.

[0026] The invention provides an imidazolium polyester polyol, comprising the following raw materials: imidazolium bromide diol and imidazolium sulfonate dibasic acid, wherein the molar ratio of imidazolium sulfonate dibasic acid to imidazolium bromide diol is 1 moL:(1.05-1.55) moL; wherein the raw materials of imidazolium bromide diol comprise N-imidazole compounds and dibromodiol substances in a molar ratio of (2.01-2.1) moL:1 moL, the raw materials of imidazolium sulfonate dibasic acid comprise dibasic acid grafted with imidazole groups and 1,3-propanesulfone in a molar ratio of 1 moL:1 moL, and the dibasic acid grafted with imidazole groups comprises 1,3,5-pentanetricarboxylic acid and imidazole alcohol substances in a molar ratio of 1 moL:1 moL.

[0027] The present invention provides a method for preparing an imidazolium polyester polyol, comprising the following steps: S1, mixing an N-imidazole compound and a dibromodiol substance in a molar ratio of (2.01-2.1) mol:1 mol, adding a solvent, and reacting the mixture in a CO 2 After reacting at 60-90° C. in an atmosphere for 5-24 hours, the mixture is subjected to rotary evaporation to remove impurities to obtain imidazolium bromide diol. The reaction formula of the process is as follows; the N-imidazole compound is one or more of N-methylimidazole, N-ethylimidazole, N-n-propylimidazole, N-isopropylimidazole, N-n-butylimidazole, N-tert-butylimidazole, and N-phenylimidazole; the dibromodiol substance is one or more of 2,3-dibromo-1,4-butanediol, 2,2-dibromo-1,4-butanediol, 2,2-dibromo-1,5-pentanediol, dibromoneopentyl glycol, 3,6-dibromophenanthrene-9,10-diol, and 1,8-dibromo-2,7-dihydroxynaphthalene; the solvent is one or more of tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, 1,3-dioxolane, and 1,4-dioxane;

[0028]

[0029] S2, using 1,3,5-pentanetricarboxylic acid and imidazole alcohols in a molar ratio of 1 mol:1 mol to react at 140-180° C. for 1-8 h to remove impurities by rotary evaporation to form a dibasic acid grafted with an imidazole group, the reaction formula is as follows, the imidazole alcohols are 1-hydroxymethylimidazole, 1-(2-hydroxyethyl)imidazole, 1-(3-hydroxypropyl)-1H-imidazole, 2-(1H-imidazol-1-yl)propane-1-ol, 1-(2-hydroxypropyl)imidazole, 2-(2-methyl-1H-imidazol-1-yl)ethanol One or more;

[0030]

[0031] S3, the dibasic acid grafted with imidazole groups obtained in S2 is reacted with 1,3-propane sultone at a molar ratio of 1 mol:1 mol to obtain imidazole sulfonate dibasic acid after removing impurities. The reaction formula is as follows:

[0032]

[0033] S4. Add the imidazole sulfonate onium dibasic acid obtained in S3 and the imidazole bromine onium diol obtained in S1 into the reactor, react under nitrogen protection, add a metal catalyst, stop nitrogen flow, start a vacuum pump to evacuate, and react after heating. The acid value of the reaction product is ≤1.0 mg. KOH / g, cooling to room temperature to obtain imidazolium polyester polyol, the reaction formula is as follows, the molar ratio of imidazolium sulfonate dibasic acid to imidazolium bromine diol is 1moL:(1.05-1.55)moL; the metal catalyst is a catalyst commonly used in the synthesis of polyester polyols, which is one of dibutyltin dilaurate, stannous octoate, isopropyl titanate, tetrabutyl titanate, antimony trioxide, and zinc acetate, and the amount used is 0.05-1.5% of the total reactant mass; the reaction temperature of imidazolium sulfonate dibasic acid and imidazolium bromine diol under nitrogen protection is 140-180°C, and the reaction time is 4-10h; the vacuum degree of the reaction of imidazolium sulfonate dibasic acid and imidazolium bromine diol under vacuum environment is 0.75-0.95bar, the reaction temperature is 190-220°C, and the reaction time is 1-6h.

[0034]

[0035] The invention provides a method for preparing imidazolium polyester polyol and a polyurethane synthesized by a polyester polyol. The polyurethane comprises the following raw materials: imidazolium polyester polyol and polyethylene adipate polyol / polyether polyol in a mass ratio of 1:(5-105), a chain extender in an amount of 2-5 parts per 100 parts of the polyol, a foam stabilizer in an amount of 2-5 parts per 100 parts of the polyol, a catalyst in an amount of 0.5-1.5 parts per 100 parts of the polyol, a foaming agent in an amount of 2-5 parts per 100 parts of the polyol, and an isocyanate substance in an amount of 50-100 parts per 100 parts of the polyol.

[0036] The invention provides a method for preparing an imidazolium polyester polyol and a method for preparing a polyurethane synthesized from a polyester polyol. The method comprises the following steps: mixing the obtained imidazolium polyester polyol with polyethylene adipate polyol / polyether polyol, and mixing with a chain extender, a foam stabilizer, a catalyst and a foaming agent, wherein the mixed material is referred to as material A; adding an isocyanate substance into a container, which is referred to as material B; pouring the material B into a reactor containing the material A, stirring at room temperature, pouring the material into a mold for free foaming, and placing the material in an oven for ripening after the foam surface is no longer sticky. The molecular weight of the imidazolium polyester polyol is 500-10000, and the hydroxyl value is 11mgKOH / g-220mgKOH / g; the molar ratio of the imidazolium polyester polyol to the polyethylene adipate polyol / polyether polyol is 1moL:(10-1000)moL, the chain extender is one of ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, and 1,5-pentanediol; the foam stabilizer is silicone oil M-8860; the catalyst is one of dibutyltin dilaurate, diethanolamine, triethanolamine, N-ethylmorpholine, N-methylmorpholine, and A-33; the isocyanate substance is one of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate.

[0037]

[0038] Example 1

[0039] S1. Weigh 16.5 g (0.201 mol) of N-methylimidazole and 24.8 g (0.1 mol) of 2,3-dibromo-1,4-butanediol into a reactor, add 50 g of tetrahydrofuran solvent, and then pass N 2 , in N 2 Under protection, the reactor was heated to 60°C for reaction for 24 hours, and impurities were removed by rotary evaporation to obtain imidazolium bromide diol.

[0040] S2. Weigh 20.4 g (0.1 mol) of 1,3,5-pentanetricarboxylic acid and 9.8 g (0.1 mol) of 1-hydroxymethylimidazole and add them into the reactor, and pass nitrogen for 10 minutes. Heat the reactor to 140° C. under nitrogen protection and react for 8 hours to obtain a dibasic acid with a grafted imidazole group.

[0041] S3. Continue to weigh 12.2 g (0.1 mol) of 1,3-propane sultone and add it to the reactor to react with the dibasic acid grafted with imidazole groups obtained in S2. Heat the reactor to 60° C. and react for 24 h. Remove impurities by rotary evaporation to obtain imidazole onium sulfonate dibasic acid.

[0042] S4, weigh 4.34g (0.0105mol) of imidazole bromide diol obtained in S1 and 4.06g (0.01mol) of imidazole sulfonate dibasic acid obtained in S3 and add them to the reactor. Heat the reactor to 140°C in a nitrogen environment and react for 10h. Then add 0.004g (0.05% of the total reactant mass) of catalyst dibutyltin dilaurate to the reactor, stop nitrogen flow, turn on the vacuum pump to a vacuum degree of 0.75bar, and heat the reactor to 190°C for 6h. Take samples for acid value analysis. When the acid value is ≤1.0mg KOH / g, the reaction was considered to be complete, the product was poured into a glass dish, cooled naturally to room temperature, and dried to obtain imidazolium polyester polyol. The molecular weight of the polyester polyol was measured to be 10000 and the hydroxyl value was 11mg KOH / g.

[0043] Example 2

[0044] S1, weigh 19.3g (0.201mol) of N-ethylimidazole and 24.8g (0.1mol) of 2,2-dibromo-1,4-butanediol and add them to the reactor, add 50g of solvent N,N-dimethylformamide and then pass N 2 , in N 2 Under protection, the reactor was heated to 60° C. for reaction for 24 h, and impurities were removed by rotary evaporation to obtain imidazolium bromide diol.

[0045] S2. Weigh 20.4 g (0.1 mol) of 1,3,5-pentanetricarboxylic acid and 11.2 g (0.1 mol) of 1-(2-hydroxyethyl)imidazole and add them into the reactor, and pass nitrogen for 10 minutes. Heat the reactor to 140° C. under nitrogen protection and react for 8 hours to obtain a dibasic acid with a grafted imidazole group.

[0046] S3. Continue to weigh 12.2 g (0.1 mol) of 1,3-propane sultone and add it to the reactor to react with the dibasic acid grafted with imidazole groups obtained in S2. Heat the reactor to 60° C. and react for 24 h. Remove impurities by rotary evaporation to obtain imidazole onium sulfonate dibasic acid.

[0047] S4, weigh 4.63g (0.0105mol) of imidazole bromide diol obtained in S1 and 4.2g (0.01mol) of imidazole sulfonate dibasic acid obtained in S3 and add them to the reactor. Heat the reactor to 140°C in a nitrogen environment and react for 9.5h. Then add 0.0045g (0.05% of the total reactant mass) of catalyst stannous octoate to the reactor, stop nitrogen flow, turn on the vacuum pump to a vacuum degree of 0.75bar, and heat the reactor to 195°C for 5h. Take samples for acid value analysis. When the acid value is ≤1.0mg KOH / g, the reaction was considered to be complete, the product was poured into a glass dish, cooled naturally to room temperature, and dried to obtain an imidazolium-containing polyester polyol. The molecular weight of the polyester polyol was measured to be 9127 and the hydroxyl value was 12.05 mg KOH / g.

[0048] Example 3

[0049] S1. Weigh 25.33 g (0.204 mol) of N-n-butylimidazole and 36.8 g (0.1 mol) of 3,6-dibromophenanthrene-9,10-diol into a reactor, add 50 g of solvent 1,3-dioxolane, introduce nitrogen, then heat the reactor to 70°C and react for 16 hours. Remove impurities by rotary evaporation to obtain imidazolium bromodiol.

[0050] S2. Weigh 20.4 g (0.1 mol) of 1,3,5-pentanetricarboxylic acid and 12.62 g (0.1 mol) of 1-(2-hydroxypropyl)imidazole and add them into the reactor, and pass nitrogen for 10 minutes. Heat the reactor to 155° C. under nitrogen protection and react for 6 hours to obtain a dibasic acid with a grafted imidazole group.

[0051] S3. Continue to weigh 12.2 g (0.1 mol) of 1,3-propane sultone and add it into the reactor to react with the grafted imidazole group dibasic acid obtained in S2. Heat the reactor to 70° C. and react for 16 h. Remove impurities by rotary evaporation to obtain imidazole sulfonate dibasic acid.

[0052] S4, weigh 7.45g (0.012mol) of imidazole bromide diol obtained in S1 and 4.34g (0.01mol) of imidazole sulfonate dibasic acid obtained in S3 and add them to the reactor, heat the reactor to 155°C under nitrogen environment and react for 8h, then add 0.059g (0.5% of the total reactant mass) of catalyst antimony trioxide into the reactor, stop nitrogen flow, turn on the vacuum pump to a vacuum degree of 0.9bar, heat the reactor to 210°C and react for 2h. Take samples for acid value analysis, when the acid value is ≤1.0mg KOH / g, the reaction was considered to be complete, the product was poured into a glass dish, cooled naturally to room temperature, and dried to obtain imidazolium polyester polyol. The molecular weight of the polyester polyol was measured to be 6126 and the hydroxyl value was 17.96mg KOH / g.

[0053] Example 4

[0054] S1. Weigh 25.46 g (0.205 mol) of N-tert-butyl imidazole and 31.8 g (0.1 mol) of 1,8-dibromo-2,7-dihydroxynaphthalene into a reactor, add 50 g of solvent 1,4-dioxane, introduce nitrogen, then heat the reactor to 70°C and react for 16 hours. Remove impurities by rotary evaporation to obtain imidazole bromo-onium diol.

[0055] S2. Weigh 20.4 g (0.1 mol) of 1,3,5-pentanetricarboxylic acid and 12.62 g (0.1 mol) of 2-(2-methyl-1H-imidazol-1-yl)ethanol and add them to the reactor, and pass nitrogen for 10 minutes. Heat the reactor to 160° C. under nitrogen protection and react for 5 hours to obtain a dibasic acid with a grafted imidazole group.

[0056] S3. Continue to weigh 12.2 g (0.1 mol) of 1,3-propane sultone and add it into the reactor to react with the grafted imidazole group dibasic acid obtained in S2. Heat the reactor to 70° C. and react for 16 h. Remove impurities by rotary evaporation to obtain imidazole sulfonate dibasic acid.

[0057] S4, weigh 7.16g (0.0125mol) of imidazole bromide diol obtained in S1 and 4.34g (0.01mol) of imidazole sulfonate dibasic acid obtained in S3 and add them to the reactor. Heat the reactor to 160°C under nitrogen environment and react for 7.5h. Then add 0.086g (0.75% of the total reactant mass) of catalyst zinc acetate to the reactor, stop nitrogen flow, turn on the vacuum pump to a vacuum degree of 0.95bar, heat the reactor to 220°C and react for 1h. Take samples for acid value analysis. When the acid value is ≤1.0mg KOH / g, the reaction was considered to be complete, the product was poured into a glass dish, cooled naturally to room temperature, and dried to obtain imidazolium polyester polyol. The molecular weight of the polyester polyol was measured to be 5012 and the hydroxyl value was 21.96mg KOH / g.

[0058] Example 5

[0059] S1. Weigh 27.1 g (0.207 mol) of N-phenylimidazole and 36.8 g (0.1 mol) of 3,6-dibromophenanthrene-9,10-diol into a reactor, add 50 g of solvent N,N-dimethylformamide, introduce nitrogen, heat the reactor to 75° C. under nitrogen protection, react for 12 h, remove impurities by rotary evaporation, and obtain imidazolium bromodiol.

[0060] S2. Weigh 20.4 g (0.1 mol) of 1,3,5-pentanetricarboxylic acid and 12.62 g (0.1 mol) of 1-(2-hydroxypropyl)imidazole and add them into the reactor, and pass nitrogen for 10 minutes. Heat the reactor to 170° C. under nitrogen protection and react for 3 hours to obtain a dibasic acid with a grafted imidazole group.

[0061] S3. Continue to weigh 12.2 g (0.1 mol) of 1,3-propane sultone and add it into the reactor to react with the grafted imidazole group dibasic acid obtained in S2. Heat the reactor to 80° C. and react for 12 h. Remove impurities by rotary evaporation to obtain imidazole sulfonate dibasic acid.

[0062] S4, weigh 7.65g (0.0135mol) of imidazole bromide diol obtained in S1 and 4.34g (0.01mol) of imidazole sulfonate dibasic acid obtained in S3 and add them to the reactor. Heat the reactor to 170°C under nitrogen atmosphere and react for 6.5h. Then add 0.12g (1% of the total reactant mass) of catalyst stannous octoate to the reactor, stop nitrogen flow, turn on the vacuum pump to a vacuum degree of 0.8bar, heat the reactor to 195°C and react for 5h. Take samples for acid value analysis. When the acid value is ≤1.0mg KOH / g, the reaction was considered to be complete, the product was poured into a glass dish, cooled naturally to room temperature, and dried to obtain imidazolium polyester polyol. The molecular weight of the polyester polyol was measured to be 3495 and the hydroxyl value was 31.47 mg KOH / g.

[0063] Example 6

[0064] S1. Weigh 22.91 g (0.208 mol) of N-n-propyl imidazole and 26.2 g (0.1 mol) of dibromoneopentyl glycol and add them into a reactor. Add 50 g of solvent N,N-dimethylacetamide and introduce nitrogen. Heat the reactor to 80° C. under nitrogen protection and react for 8 h. Remove impurities by rotary evaporation to obtain imidazole bromo-onium diol.

[0065] S2. Weigh 20.4 g (0.1 mol) of 1,3,5-pentanetricarboxylic acid and 12.62 g (0.1 mol) of 2-(1H-imidazol-1-yl)propane-1-ol into a reactor and pass nitrogen for 10 min. Heat the reactor to 175° C. under nitrogen protection and react for 2 h to obtain a dibasic acid with a grafted imidazole group.

[0066] S3. Continue to weigh 12.2 g (0.1 mol) of 1,3-propane sultone and add it into the reactor to react with the grafted imidazole group dibasic acid obtained in S2. Heat the reactor to 80° C. and react for 8 h. Remove impurities by rotary evaporation to obtain imidazole sulfonate dibasic acid.

[0067] S4, weigh 6.86g (0.014mol) of imidazole bromide diol obtained in S1 and 4.34g (0.01mol) of imidazole sulfonate dibasic acid obtained in S3 and add them to the reactor, heat the reactor to 170℃ under nitrogen environment and react for 6h, then add 0.134g (1.2% of the total reactant mass) of catalyst isopropyl titanate into the reactor, stop nitrogen flow, turn on the vacuum pump to a vacuum degree of 0.85bar, heat the reactor to 200℃ and react for 4h. Take samples for acid value analysis, when the acid value is ≤1.0mg KOH / g, the reaction was considered to be complete, the product was poured into a glass dish, cooled naturally to room temperature, and dried to obtain imidazolium polyester polyol. The molecular weight of the polyester polyol was measured to be 2343 and the hydroxyl value was 46.95mg KOH / g.

[0068] Example 7

[0069] S1, weigh 23.02g (0.209mol) of N-isopropyl imidazole and 26.2g (0.1mol) of 2,2-dibromo-1,5-pentanediol and add them to the reactor, add 50g of solvent N-methylpyrrolidone and then pass CO 2 , in CO 2 Under protection, the reactor was heated to 65° C. and reacted for 12 h. Impurities were removed by rotary evaporation to obtain imidazolium bromide diol.

[0070] S2. Weigh 20.4 g (0.1 mol) of 1,3,5-pentanetricarboxylic acid and 12.62 g (0.1 mol) of 1-(3-hydroxypropyl)-1H-imidazole and add them into the reactor, and pass nitrogen for 10 minutes. Heat the reactor to 175° C. under nitrogen protection and react for 2 hours to obtain a dibasic acid with a grafted imidazole group.

[0071] S3. Continue to weigh 12.2 g (0.1 mol) of 1,3-propane sultone and add it into the reactor to react with the grafted imidazole group dibasic acid obtained in S2. Heat the reactor to 85° C. and react for 8 h. Remove impurities by rotary evaporation to obtain imidazole sulfonate dibasic acid.

[0072] S4, weigh 7.14g (0.0145mol) of imidazole bromide diol obtained in S1 and 4.34g (0.01mol) of imidazole sulfonate dibasic acid obtained in S3 and add them to the reactor. Heat the reactor to 175°C under nitrogen environment and react for 5.5h. Then add 0.144g (1.25% of the total reactant mass) of catalyst tetrabutyl titanate to the reactor, stop nitrogen flow, turn on the vacuum pump to a vacuum degree of 0.9bar, and heat the reactor to 205°C for 3h. Take samples for acid value analysis. When the acid value is ≤1.0mg KOH / g, the reaction was considered to be complete, the product was poured into a glass dish, cooled naturally to room temperature, and dried to obtain imidazolium polyester polyol. The molecular weight of the polyester polyol was measured to be 1728 and the hydroxyl value was 63.66 mg KOH / g.

[0073] Example 8

[0074] S1, weigh 26.08g (0.21mol) of N-n-butyl imidazole and 24.8g (0.1mol) of 2,2-dibromo-1,4-butanediol and add them into the reactor, add 50g of solvent 1,3-dioxolane and then introduce CO 2 , in CO 2 Under protection, the reactor was heated to 70°C for 8 hours, and impurities were removed by rotary evaporation to obtain imidazolium bromide diol.

[0075] S2. Weigh 20.4 g (0.1 mol) of 1,3,5-pentanetricarboxylic acid and 11.21 g (0.1 mol) of 1-(2-hydroxyethyl)imidazole and add them to the reactor, and pass nitrogen for 10 minutes. Heat the reactor to 180° C. under nitrogen protection and react for 1 hour to obtain a dibasic acid with a grafted imidazole group.

[0076] S3. Continue to weigh 12.2 g (0.1 mol) of 1,3-propane sultone and add it into the reactor to react with the dibasic acid grafted with imidazole groups obtained in S2. Heat the reactor to 90° C. and react for 5 h. Remove impurities by rotary evaporation to obtain imidazole onium sulfonate dibasic acid.

[0077] S4, weigh 7.63g (0.015mol) of imidazole bromide diol obtained in S1 and 4.2g (0.01mol) of imidazole sulfonate dibasic acid obtained in S3 and add them into the reactor, heat the reactor to 180°C under nitrogen environment and react for 5h, then add 0.177g (1.5% of the total reactant mass) of catalyst antimony trioxide into the reactor, stop nitrogen flow, turn on the vacuum pump to a vacuum degree of 0.95bar, heat the reactor to 210°C and react for 2h. Take samples for acid value analysis, when the acid value is ≤1.0mg KOH / g, the reaction was considered to be complete, the product was poured into a glass dish, cooled naturally to room temperature, and dried to obtain imidazolium polyester polyol. The molecular weight of the polyester polyol was measured to be 1299 and the hydroxyl value was 84.68 mg KOH / g.

[0078] Example 9

[0079] S1, weigh 26.08g (0.21mol) of N-tert-butyl imidazole and 24.8g (0.1mol) of 2,3-dibromo-1,4-butanediol and add them into the reactor, add 50g of solvent 1,3-dioxolane and then introduce CO 2 , in CO 2 Under protection, the reactor was heated to 70°C for 8 hours, and impurities were removed by rotary evaporation to obtain imidazolium bromide diol.

[0080] S2. Weigh 20.4 g (0.1 mol) of 1,3,5-pentanetricarboxylic acid and 9.81 g (0.1 mol) of 1-(2-hydroxyethyl)imidazole and add them to the reactor, and pass nitrogen for 10 minutes. Heat the reactor to 180° C. under nitrogen protection and react for 1 hour to obtain a dibasic acid with a grafted imidazole group.

[0081] S3. Continue to weigh 12.2 g (0.1 mol) of 1,3-propane sultone and add it into the reactor to react with the dibasic acid grafted with imidazole groups obtained in S2. Heat the reactor to 90° C. and react for 5 h. Remove impurities by rotary evaporation to obtain imidazole onium sulfonate dibasic acid.

[0082] S4, weigh 7.89g (0.0155mol) of imidazole bromine diol obtained in S1 and 4.06g (0.01mol) of imidazole sulfonate dibasic acid obtained in S3 and add them to the reactor, heat the reactor to 180°C under nitrogen environment and react for 4h, then add 0.18g (1.5% of the total reactant mass) of catalyst zinc acetate into the reactor, stop nitrogen flow, turn on the vacuum pump to a vacuum degree of 0.95bar, heat the reactor to 220°C and react for 1h. Take samples for acid value analysis, when the acid value is ≤1.0mg KOH / g, the reaction was considered to be complete, the product was poured into a glass dish, cooled naturally to room temperature, and dried to obtain imidazolium polyester polyol. The molecular weight of the polyester polyol was measured to be 500 and the hydroxyl value was 22.0mg KOH / g.

[0083] In the reaction of N-imidazoles with dibromodiols, CO 2 The hyperconjugation effect between the bromine group and the hydroxyl group in dibromodiol substances is weakened, the reaction rate is accelerated, and the reaction time is shortened.

[0084] Comparative Example 1

[0085] S1. Weigh 16.5 g (0.201 mol) of N-methylimidazole and 24.8 g (0.1 mol) of 2,3-dibromo-1,4-butanediol into a reactor, add 50 g of tetrahydrofuran solvent and introduce nitrogen, heat the reactor to 60° C. under nitrogen protection, react for 15 h, remove impurities by rotary evaporation, and obtain imidazolium bromodiol.

[0086] S2. Weigh 20.4 g (0.1 mol) of 1,3,5-pentanetricarboxylic acid and 9.8 g (0.1 mol) of 1-hydroxymethylimidazole and add them into the reactor, and pass nitrogen for 10 minutes. Heat the reactor to 140° C. under nitrogen protection and react for 1 hour to obtain a dibasic acid with a grafted imidazole group.

[0087] S3, weigh 4.34g (0.0105mol) of imidazolium bromide diol obtained by S1, 3.02g (0.01mol) of dibasic acid with grafted imidazole group obtained by S2, add them into the reactor, heat the reactor to 140℃ in nitrogen environment and react for 4h, then add 0.004g (0.05% of the total reactant mass) of catalyst dibutyltin dilaurate into the reactor, stop nitrogen flow, open the vacuum pump to the vacuum degree of 0.75bar, heat the reactor to 190℃ and react for 1h. Take samples for acid value analysis, when the acid value is ≤1.0mg KOH / g, the reaction was considered to be complete, the product was poured into a glass dish, cooled naturally to room temperature, and dried to obtain a polyester polyol containing an imidazolium bromide ion structure and a grafted imidazole group. The molecular weight of the polyester polyol was measured to be 9456 and the hydroxyl value was 11.63mg KOH / g.

[0088] Comparative Example 2

[0089] S1. Weigh 20.4 g (0.1 mol) of 1,3,5-pentanetricarboxylic acid and 11.2 g (0.1 mol) of 1-(2-hydroxyethyl)imidazole into a reactor and pass nitrogen for 10 min. Heat the reactor to 140° C. under nitrogen protection and react for 1 h to obtain a dibasic acid with a grafted imidazole group.

[0090] S2. Continue to weigh 12.2 g (0.1 mol) of 1,3-propane sultone and add it to the reactor to react with the dibasic acid grafted with imidazole groups obtained in S2. Heat the reactor to 60° C. and react for 5 h. Remove impurities by rotary evaporation to obtain imidazole onium sulfonate dibasic acid.

[0091] S3, weigh 0.652g (0.0105mol) of ethylene glycol and 4.2g (0.01mol) of the dibasic acid containing the imidazolium ion structure obtained in S2 and add them to the reactor. Heat the reactor to 140°C in a nitrogen environment and react for 5h. Then add 0.0024g (0.05% of the total reactant mass) of catalyst stannous octoate to the reactor, stop nitrogen flow, turn on the vacuum pump to a vacuum degree of 0.75bar, and heat the reactor to 195°C for 2h. Take samples for acid value analysis. When the acid value is ≤1.0mg KOH / g, the reaction was considered to be complete, the product was poured into a glass dish, cooled naturally to room temperature, and dried to obtain a polyester polyol containing only an imidazole sulfonate onium ion structure. The molecular weight of the polyester polyol was measured to be 8356 and the hydroxyl value was 13.16 mg KOH / g.

[0092] Comparative Example 3

[0093] S1. Weigh 20.4 g (0.1 mol) of 1,3,5-pentanetricarboxylic acid and 12.62 g (0.1 mol) of 1-(3-hydroxypropyl)-1H-imidazole into a reactor and pass nitrogen for 10 min. Heat the reactor to 145° C. and react for 2 h under nitrogen protection to obtain a dibasic acid with a grafted imidazole group.

[0094] S2, weigh 0.68g (0.011mol) of ethylene glycol and 4.34g (0.01mol) of the dibasic acid with grafted imidazole groups obtained in S1 and add them to the reactor. Heat the reactor to 145°C in a nitrogen environment and react for 5.5h. Then add 0.005g (0.1% of the total reactant mass) of catalyst isopropyl titanate to the reactor, stop nitrogen flow, turn on the vacuum pump to a vacuum degree of 0.8bar, and heat the reactor to 200°C for 3h. Take samples for acid value analysis. When the acid value is ≤1.0mg KOH / g, the reaction was considered to be complete, the product was poured into a glass dish, cooled naturally to room temperature, and dried to obtain only the polyester polyol grafted with imidazole groups. The molecular weight of the polyester polyol was measured to be 7911 and the hydroxyl value was 13.9mg KOH / g.

[0095] Application Example 1

[0096] S5. Weigh 5 g of the imidazolium polyester polyol prepared in Example 1, 25 g of polyethylene adipate, 0.6 g (2 parts / 100 parts of polyol) of ethylene glycol, 0.6 g (2 parts / 100 parts of polyol) of M-8860, 0.15 g (0.5 parts / 100 parts of polyol) of dibutyltin dilaurate, and 0.6 g (2 parts / 100 parts of polyol) of water in a reactor, place the reactor in a 60°C water bath, stir at 800 rpm for 5 min to mix the raw materials evenly, and record the mixed material as material A. Weigh 15 g (50 parts / 100 parts of polyol) of toluene diisocyanate in a container, record it as material B.

[0097] S6. Pour material B into the reactor containing material A and stir vigorously at 1000 rpm for 10 seconds. When the materials are observed to be evenly mixed and white in color, pour them into the mold and foam freely. When the foam surface stops rising and is not sticky, place it in a 40°C oven for 16 hours.

[0098] It was determined that after the prepared polyurethane foam was in contact with Escherichia coli and Staphylococcus aureus for 4 hours, the live colonies on the surface of the foam completely disappeared, indicating that polyurethane has good antibacterial properties; it was determined that after the prepared polyurethane foam was in contact with the coronavirus, the virus infection rate on the surface of the polyurethane foam was 11%, indicating that polyurethane has good antiviral properties.

[0099] Application Example 2

[0100] S5. Weigh 0.5 g of the imidazolium polyester polyol prepared in Example 2, 50 g of polyethylene adipate, 1.515 g (3 parts / 100 parts of polyol) of 1,2-propylene glycol, 1.515 g (3 parts / 100 parts of polyol) of M-8860, 0.25 g (0.5 parts / 100 parts of polyol) of diethanolamine, and 1.515 g (3 parts / 100 parts of polyester polyol) of water into a reactor, place the reactor in a 60°C water bath, stir at 800 rpm for 6 min to mix the raw materials evenly, and record the mixed material as material A. Weigh 27.775 g (55 parts / 100 parts of polyol) of diphenylmethane diisocyanate into a container, record it as material B.

[0101] S6. Pour material B into the reactor containing material A and stir vigorously at 1000 rpm for 12 seconds. When the materials are observed to be evenly mixed and white in color, pour them into the mold and foam freely. When the foam surface stops rising and is not sticky, place it in a 40°C oven for 16 hours.

[0102] It was determined that after the prepared polyurethane foam was in contact with Escherichia coli and Staphylococcus aureus for 4 hours, the live colonies on the surface of the foam completely disappeared, indicating that polyurethane has good antibacterial properties; it was determined that after the prepared polyurethane foam was in contact with the coronavirus, the virus infection rate on the surface of the polyurethane foam was 12%, indicating that polyurethane has good antiviral properties.

[0103] Application Example 3

[0104] S5, weigh 0.25g of the imidazolium polyester polyol obtained in Example 5, 150g of polyether polyol, 3.005g (2 parts / 100 parts of polyol) of ethylene glycol, 3.005g (2 parts / 100 parts of polyol) of M-8860, 1.503g (1 part / 100 parts of polyol) of N-ethylmorpholine, 3.005g (2 parts / 100 parts of polyol) of water in a reactor, place the reactor in a 70°C water bath, stir at 950rpm for 9min to mix the raw materials evenly, and record the mixed material as material A. Weigh 105.175g (70 parts / 100 parts of polyol) of toluene diisocyanate in a container, record it as material B.

[0105] S6. Pour material B into the reactor containing material A and stir vigorously at 1150 rpm for 18 seconds. When the materials are observed to be evenly mixed and white in color, pour them into the mold for free foaming. When the foam surface stops rising and is not sticky, place it in a 55°C oven for aging for 20 hours.

[0106] It was determined that after the prepared polyurethane foam was in contact with Escherichia coli and Staphylococcus aureus for 5 hours, the live colonies on the surface of the foam completely disappeared, indicating that polyurethane has good antibacterial properties; it was determined that after the prepared polyurethane foam was in contact with the coronavirus, the virus infection rate on the surface of the polyurethane foam was 16%, indicating that polyurethane has good antiviral properties.

[0107] Application Example 4

[0108] S5. Weigh 0.25 g of the imidazolium polyester polyol prepared in Example 6, 200 g of polyether polyol, 6.01 g (3 parts / 100 parts of polyol) of 1,2-propylene glycol, 6.01 g (3 parts / 100 parts of polyol) of M-8860, 2 g (1 part / 100 parts of polyol) of A-33, and 6.01 g (3 parts / 100 parts of polyol) of water into a reactor, place the reactor in a 70°C water bath, stir at 1000 rpm for 10 min to mix the raw materials evenly, and record the mixed material as material A. Weigh 150.19 g (75 parts / 100 parts of polyol) of diphenylmethane diisocyanate into a container, and record it as material B.

[0109] S6. Pour material B into the reactor containing material A and stir vigorously at 1200 rpm for 20 seconds. When the materials are observed to be evenly mixed and white in color, pour them into the mold for free foaming. When the foam surface stops rising and is not sticky, place it in a 60°C oven for aging for 22 hours.

[0110] It was determined that after the prepared polyurethane foam was in contact with Escherichia coli and Staphylococcus aureus for 5 hours, the live colonies on the surface of the foam completely disappeared, indicating that polyurethane has good antibacterial properties; it was determined that after the prepared polyurethane foam was in contact with the coronavirus, the virus infection rate on the surface of the polyurethane foam was 13%, indicating that polyurethane has good antiviral properties.

[0111] Application Example 5

[0112] S5. Weigh 0.1 g of the imidazolium polyester polyol obtained in Example 8, 200 g of polyether polyol, 10 g (5 parts / 100 parts of polyol) of 1,5-pentanediol, 10 g (5 parts / 100 parts of polyol) of M-8860, 2.5 g (1.25 parts / 100 parts of polyol) of diethanolamine, and 10 g (5 parts / 100 parts of polyol) of water into a reactor, place the reactor in a 75°C water bath, stir at 1100 rpm for 12 min to mix the raw materials evenly, and record the mixed material as material A. Weigh 170 g (85 parts / 100 parts of polyol) of isophorone diisocyanate into a container, record it as material B.

[0113] S6. Pour material B into the reactor containing material A and stir vigorously at 1300 rpm for 24 seconds. When the materials are observed to be evenly mixed and white in color, pour them into the mold and foam freely. When the foam surface stops rising and is not sticky, place it in a 70°C oven for aging for 24 hours.

[0114] It was determined that after the prepared polyurethane foam was in contact with Escherichia coli and Staphylococcus aureus for 5.5 hours, the live colonies on the surface of the foam completely disappeared, indicating that polyurethane has good antibacterial properties; it was determined that after the prepared polyurethane foam was in contact with the coronavirus, the virus infection rate on the surface of the polyurethane foam was 22%, indicating that polyurethane has good antiviral properties.

[0115] Application Example 6

[0116] S5, weigh 0.05g of imidazolium polyester polyol prepared in Example 9, 200g of polyethylene adipate, 4g (2 parts / 100 parts of polyol) of ethylene glycol, 4g (2 parts / 100 parts of polyol) of M-8860, 3g (1.5 parts / 100 parts of polyol) of triethanolamine, 4g (2 parts / 100 parts of polyol) of water in a reactor, place the reactor in a water bath at 80°C, stir at 1100rpm for 13min to mix the raw materials evenly, record the mixed material as material A. Weigh 180g (90 parts / 100 parts of polyol) of toluene diisocyanate in a container, record it as material B.

[0117] S6. Pour material B into the reactor containing material A and stir vigorously at 1350 rpm for 26 seconds. When the materials are observed to be evenly mixed and white in color, pour them into the mold for free foaming. When the foam surface stops rising and is not sticky, place it in a 75°C oven for aging for 26 hours.

[0118] It was determined that after the prepared polyurethane foam was in contact with Escherichia coli and Staphylococcus aureus for 6 hours, the live colonies on the surface of the foam completely disappeared, indicating that polyurethane has good antibacterial properties; it was determined that after the prepared polyurethane foam was in contact with the coronavirus, the virus infection rate on the surface of the polyurethane foam was 21%, indicating that polyurethane has good antiviral properties.

[0119] Application Example 10

[0120] S5. Weigh 5g of the imidazolium polyester polyol prepared in Comparative Example 1, 25g of polyethylene adipate, 0.6g (2 parts / 100 parts of polyol) of ethylene glycol, 0.6g (2 parts / 100 parts of polyol) of M-8860, 0.15g (0.5 parts / 100 parts of polyol) of dibutyltin dilaurate, and 0.6g (2 parts / 100 parts of polyol) of water in a reactor, place the reactor in a 60°C water bath, stir at 800rpm for 5min to mix the raw materials evenly, and record the mixed material as material A. Weigh 15g (50 parts / 100 parts of polyol) of toluene diisocyanate in a container, record it as material B.

[0121] S6. Pour material B into the reactor containing material A and stir vigorously at 1000 rpm for 10 seconds. When the materials are observed to be evenly mixed and white in color, pour them into the mold and foam freely. When the foam surface stops rising and is not sticky, place it in a 40°C oven for 16 hours.

[0122] It was determined that after the prepared polyurethane foam was in contact with Escherichia coli and Staphylococcus aureus for 12 hours, the live colonies on the surface of the foam completely disappeared, indicating that the antibacterial performance of the polyurethane containing imidazolium bromide structure and grafted imidazole group is general, not as good as the polyurethane grafted with imidazolium bromide structure and imidazole sulfonate structure; it was determined that after the prepared polyurethane foam was in contact with the coronavirus, the virus infection rate on the surface of the polyurethane foam was 35%, indicating that the polyurethane containing imidazolium bromide ion structure and grafted imidazole group has general antiviral performance, weaker than the polyurethane grafted with imidazolium bromide structure and imidazole sulfonate structure.

[0123] Application Example 11

[0124] S5. Weigh 5g of the imidazolium polyester polyol prepared in Comparative Example 2, 25g of polyethylene adipate, 0.6g (2 parts / 100 parts of polyol) of ethylene glycol, 0.6g (2 parts / 100 parts of polyol) of M-8860, 0.15g (0.5 parts / 100 parts of polyol) of dibutyltin dilaurate, and 0.6g (2 parts / 100 parts of polyol) of water in a reactor, place the reactor in a 60°C water bath, stir at 800rpm for 5min to mix the raw materials evenly, and record the mixed material as material A. Weigh 15g (50 parts / 100 parts of polyol) of toluene diisocyanate in a container, record it as material B.

[0125] S6. Pour material B into the reactor containing material A and stir vigorously at 1000 rpm for 10 seconds. When the materials are observed to be evenly mixed and white in color, pour them into the mold and foam freely. When the foam surface stops rising and is not sticky, place it in a 40°C oven for 16 hours.

[0126] It was determined that after the prepared polyurethane foam was in contact with Escherichia coli and Staphylococcus aureus for 24 hours, the live colonies on the surface of the foam completely disappeared, indicating that the polyurethane containing only imidazole sulfonate structure has poor antibacterial performance, which is not as good as the polyurethane grafted with imidazole bromide structure and imidazole sulfonate structure; it was determined that after the prepared polyurethane foam was in contact with the coronavirus, the virus infection rate on the surface of the polyurethane foam was 41%, indicating that the polyurethane containing only imidazole sulfonate ion structure has general antiviral performance, which is not as good as the polyurethane grafted with imidazole bromide structure and imidazole sulfonate structure.

[0127] Application Example 12

[0128] S5. Weigh 5g of the imidazolium polyester polyol prepared in Comparative Example 3, 25g of polyethylene adipate, 0.6g (2 parts / 100 parts of polyol) of ethylene glycol, 0.6g (2 parts / 100 parts of polyol) of M-8860, 0.15g (0.5 parts / 100 parts of polyol) of dibutyltin dilaurate, and 0.6g (2 parts / 100 parts of polyol) of water in a reactor, place the reactor in a 60°C water bath, stir at 800rpm for 5min to mix the raw materials evenly, and record the mixed material as material A. Weigh 15g (50 parts / 100 parts of polyol) of toluene diisocyanate in a container, record it as material B.

[0129] S6. Pour material B into the reactor containing material A and stir vigorously at 1000 rpm for 10 seconds. When the materials are observed to be evenly mixed and white in color, pour them into the mold and foam freely. When the foam surface stops rising and is not sticky, place it in a 40°C oven for 16 hours.

[0130] It was determined that after the prepared polyurethane foam was in contact with Escherichia coli and Staphylococcus aureus for 16 hours, the live colonies on the surface of the foam completely disappeared, indicating that the antibacterial performance of the polyurethane with only grafted imidazole groups is average, not as good as the polyurethane grafted with imidazolium bromide structure and imidazole sulfonate structure; it was determined that after the prepared polyurethane foam was in contact with the coronavirus, the virus infection rate on the surface of the polyurethane foam was 51%, indicating that the polyurethane with only grafted imidazole groups has no antiviral performance, not as good as the polyurethane grafted with imidazolium bromide structure and imidazole sulfonate structure.

[0131] Application Example 13

[0132] Chemical resistance tests were conducted in 99% pure tetrahydrofuran, 0.5% aqueous NaOH solution, 10% aqueous HCl solution, and 15% aqueous NaCl solution. 1 g of polyurethane was kept in a 100 mL amber glass bottle containing the above media at room temperature. After 10 days of testing, the percentage of weight loss was measured as Figure 2 shown.

[0133] Therefore, the present invention adopts the above-mentioned imidazolium polyester polyol and the synthesized polyurethane and the preparation method thereof to introduce the imidazolium structure into the side chain of the polyurethane, that is, a diacid containing an imidazolium sulfonate structure is reacted with a diol containing an imidazolium bromine structure to obtain a polyester polyol containing an imidazolium side chain, that is, a functional diol monomer, which is used for the synthesis of polyurethane foam. The obtained polyurethane foam contains multiple imidazolium structures on the side chain, can play an antibacterial and antiviral role, and has good mechanical properties, thermal properties and chemical resistance. The production cost is lower than that of conventional antibacterial and antiviral polyurethanes.

[0134] In the description of this specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0135] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that they can still modify or replace the technical solution of the present invention with equivalents, and these modifications or equivalent replacements cannot cause the modified technical solution to deviate from the spirit and scope of the technical solution of the present invention.

Claims

1. An imidazolium polyester polyol, characterized in that: The invention comprises the following raw materials: imidazolinium bromide diol and imidazolinium sulfonate dibasic acid, wherein the molar ratio of imidazolinium sulfonate dibasic acid to imidazolinium bromide diol is 1 mol:(1.05-1.55) mol; wherein the raw materials of imidazolinium bromide diol comprise N-imidazole compounds and dibromodiol substances in a molar ratio of (2.01-2.1) mol:1 mol, the raw materials of imidazolinium sulfonate dibasic acid comprise dibasic acid grafted with imidazole group and 1,3-propanesulfone in a molar ratio of 1 mol:1 mol, and the dibasic acid grafted with imidazole group comprises 1,3,5-pentanetricarboxylic acid and imidazole alcohol substances in a molar ratio of 1 mol:1 mol.

2. The method for preparing an imidazolium polyester polyol according to claim 1, characterized in that: The following steps are involved: S1, mixing an N-imidazole compound with a dibromodiol substance, adding a solvent, reacting in a protective gas atmosphere, and then removing impurities by rotary evaporation to obtain imidazolium bromodiol; S2, using 1,3,5-pentanetricarboxylic acid to react with an imidazole alcohol substance to form a dibasic acid grafted with an imidazole group; S3, reacting the dibasic acid grafted with an imidazole group obtained in S2 with 1,3-propanesulfone, and then removing impurities by rotary evaporation to obtain an imidazole onium sulfonate dibasic acid; S4, polycondensing the imidazolium sulfonate dibasic acid obtained in S3 with the imidazolium bromide diol obtained in S1 to obtain imidazolium polyester polyol.

3. The method for preparing an imidazolium polyester polyol according to claim 2, characterized in that: In step S1, the N-imidazole compound is one or more of N-methylimidazole, N-ethylimidazole, N-n-propylimidazole, N-isopropylimidazole, N-n-butylimidazole, N-tert-butylimidazole, and N-phenylimidazole; the dibromodiol substance is one or more of 2,3-dibromo-1,4-butanediol, 2,2-dibromo-1,4-butanediol, 2,2-dibromo-1,5-pentanediol, dibromoneopentyl glycol, 3,6-dibromophenanthrene-9,10-diol, and 1,8-dibromo-2,7-dihydroxynaphthalene; the solvent is one or more of tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, 1,3-dioxolane, and 1,4-dioxane; and the protective gas for the reaction of the N-imidazole compound with the dibromodiol substance is one or more of CO2 or N2.

4. The method for preparing an imidazolium polyester polyol according to claim 2, characterized in that: In step S2, the added imidazole alcohol substance is one or more of 1-hydroxymethylimidazole, 1-(2-hydroxyethyl)imidazole, 1-(3-hydroxypropyl)-1H-imidazole, 2-(1H-imidazol-1-yl)propane-1-ol, 1-(2-hydroxypropyl)imidazole, and 2-(2-methyl-1H-imidazol-1-yl)ethanol.

5. The method for preparing an imidazolium polyester polyol according to claim 2, characterized in that: The specific steps of step S4 are: adding the imidazolium sulfonate dibasic acid obtained in S3 and the imidazolium bromine diol obtained in S1 into a reactor, reacting under nitrogen protection, adding a metal catalyst, stopping the nitrogen flow, turning on a vacuum pump to evacuate, reacting after heating, and cooling to room temperature when the acid value of the reaction product is ≤1.0 mgKOH / g to obtain an imidazolium polyester polyol; the metal catalyst is one of dibutyltin dilaurate, stannous octoate, isopropyl titanate, tetrabutyl titanate, antimony trioxide, and zinc acetate, and the amount used is 0.05-1.5% of the total reactant mass.

6. The method for preparing an imidazolium polyester polyol according to claim 2, characterized in that: In step S1, the reaction temperature of N-imidazole compounds and dibromodiol substances is 60-90°C, and the reaction time is 5-24h; in S2, the reaction temperature of 1,3,5-pentanetricarboxylic acid and imidazole alcohol substances is 140-180°C, and the reaction time is 1-8h; in S3, the reaction temperature of the dibasic acid grafted with imidazole groups and 1,3-propanesulfonate is 60-90°C, and the reaction time is 5-24h; in S4, the reaction temperature of imidazolesulfonate dibasic acid and imidazolebromide diol under nitrogen protection is 140-180°C, and the reaction time is 4-10h; the vacuum degree of the reaction of imidazolesulfonate dibasic acid and imidazolebromide diol under vacuum environment is 0.75-0.95bar, the reaction temperature is 190-220°C, and the reaction time is 1-6h.

7. A polyurethane comprising the imidazolium polyester polyol according to claim 1, characterized in that: Includes the following raw materials: mass ratio is 1:(5-10 5 ) imidazolium polyester polyol and polyethylene adipate polyol / polyether polyol, 2-5 parts of chain extender per 100 parts of polyol, 2-5 parts of foam stabilizer per 100 parts of polyol, 0.5-1.5 parts of catalyst per 100 parts of polyol, 2-5 parts of foaming agent per 100 parts of polyol, and 50-100 parts of isocyanate per 100 parts of polyol.

8. A polyurethane according to claim 7, characterized in that: The obtained imidazolium polyester polyol is mixed with polyethylene adipate polyol / polyether polyol, and then mixed with a chain extender, a foam stabilizer, a catalyst, and a foaming agent, and the mixture is recorded as material A; an isocyanate substance is added to a container, which is recorded as material B; material B is poured into a reactor containing material A, stirred at room temperature, poured into a mold for free foaming, and placed in an oven for maturation after the foam surface is no longer sticky.

9. A polyurethane according to claim 8, characterized in that: The molecular weight of the imidazolium polyester polyol is 500-10000, and the hydroxyl value is 11mgKOH / g-220mgKOH / g; the molar ratio of the imidazolium polyester polyol to the polyethylene adipate polyol / polyether polyol is 1mol:(10-1000)mol, and the chain extender is one of ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, and 1,5-pentanediol; the foam stabilizer is silicone oil M-8860; the catalyst is one of dibutyltin dilaurate, diethanolamine, triethanolamine, N-ethylmorpholine, N-methylmorpholine, and A-33; and the isocyanate substance is one of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate.

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