Polyhydroxy gemini quaternary ammonium salt as well as preparation method and application thereof
By synthesizing polyhydroxy gemini quaternary ammonium salts as raw materials for waterborne polyurethanes, the problem of insufficient antibacterial properties of quaternary ammonium salts was solved, achieving efficient antibacterial effects and improving the stability and mechanical properties of waterborne polyurethanes.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- CHINA RES INST OF DAILY CHEM IND
- Filing Date
- 2025-12-31
- Publication Date
- 2026-04-21
Smart Images
Figure CN121895176A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of quaternary ammonium salt synthesis technology, specifically involving polyhydroxy gemini quaternary ammonium salts, their preparation methods and applications, which are used as raw materials for synthesizing cationic waterborne polyurethanes, endowing waterborne polyurethanes with excellent antibacterial and other properties. Background Technology
[0002] Human society is currently facing a serious problem of bacterial invasion, and the exploration of antibacterial methods has always been one of the most important research topics. Traditional antibacterial methods mostly rely on antibiotics, but the large-scale overuse of antibiotics in practice has led to a global crisis of antibiotic resistance. Quaternary ammonium salts (QAS) are a well-known class of highly effective antibacterial agents. Due to their persistence on treated surfaces, they possess broad-spectrum antibacterial activity and long-lasting antibacterial efficiency. Quaternary ammonium salts not only provide long-lasting contact antibacterial function, but QAS derivatives also exhibit broad-spectrum antibacterial activity against bacteria, fungi, viruses, and algae. Furthermore, QAS exhibit advantages such as customizable molecular structures, high functionality, non-volatility, long lifespan, and chemical stability; therefore, they have been widely used in the field of antibacterial materials. The antibacterial mechanism of QAS involves electrostatic attraction to the bacterial surface, disrupting the cell barrier, attacking the respiratory chain, inhibiting enzyme or protein activity, and affecting cellular metabolic processes.
[0003] Gemini quaternary ammonium salts (GQAS) consist of two cationic head groups linked by a spacer region and two hydrophobic alkyl chains. Under the same conditions, they typically exhibit better interfacial properties, such as lower critical micelle concentration (CMC), more aggregate morphologies, stronger solubilization, and enhanced surface activity. Because GQAS possesses two hydrophobic alkyl chains and two cationic head groups, they are expected to have better antibacterial properties compared to their corresponding monomers. Furthermore, GQAS demonstrates advantages such as customizable molecular structures, high functionality, non-volatility, long lifetime, and chemical stability. GQAS containing hydroxyl groups can be introduced into waterborne polyurethanes as hydrophilic chain extenders, thereby imparting antibacterial properties. Simultaneously, the hydrophilic groups in GQAS can improve the stability of waterborne polyurethane emulsions. Moreover, the introduction of Gemini quaternary ammonium salts containing multiple hydroxyl sites into waterborne polyurethanes is expected to increase the degree of crosslinking, thereby further enhancing the film properties of waterborne polyurethanes. Summary of the Invention
[0004] To prepare waterborne polyurethanes with superior performance, a series of novel polyhydroxy gemini quaternary ammonium salts were designed and synthesized from a molecular design perspective. These gemini quaternary ammonium salts contain multiple hydroxyl sites and will become an important raw material for the subsequent synthesis of cationic waterborne polyurethanes. The polyhydroxy gemini quaternary ammonium salts of this invention have advantages such as simple synthesis process, readily available raw materials, strong reaction controllability, suitability for large-scale production, and high yield. Furthermore, the purification method for subsequent products is simple.
[0005] To achieve the above objectives, the present invention employs the following technical solution:
[0006] In a first aspect, the present invention provides a polyhydroxy gemini quaternary ammonium salt, the structural formula of which is as follows:
[0007] or or
[0008] or ;
[0009] Among them, Cl - Can be replaced with Br - or I - .
[0010] Secondly, the present invention provides a method for preparing polyhydroxy gemini quaternary ammonium salts, comprising the following steps:
[0011] A hydroxyl-containing tertiary amine is quaternized with a dihaloalcohol or a dihaloalkane to obtain a polyhydroxy geminal quaternary ammonium salt. The hydroxyl-containing tertiary amine is N-methyldiethanolamine or N,N-dimethylethanolamine, the dihaloalcohol is 1,3-dichloro-2-propanol, 1,3-dibromo-2-propanol or 1,3-diiodo-2-propanol, and the dihaloalkane is 1,3-dichloropropane, 1,3-dibromopropane or 1,3-diiodopropane.
[0012] Taking 1,3-dichloropropane or 1,3-dichloro-2-propanol as examples, the synthetic route of polyhydroxy gemini quaternary ammonium salts is as follows:
[0013] .
[0014] Furthermore, the preparation method specifically includes:
[0015] A hydroxyl-containing tertiary amine is dissolved in an organic solvent and subjected to a quaternization reaction. After the reaction is completed, the organic solvent is removed to obtain a crude product. The crude product is then washed and dried to obtain the polyhydroxy gemini quaternary ammonium salt.
[0016] Furthermore, the molar ratio of the hydroxyl-containing tertiary amine to the dihaloalcohol or dihaloalkane is 1:2.
[0017] Furthermore, the organic solvent is one of anhydrous ethanol, dimethyl sulfoxide, or ultrapure water.
[0018] Furthermore, the amount of the organic solvent used is 45% of the total material.
[0019] Furthermore, the quaternization reaction is carried out at a temperature of 60–80°C for a time of 8–20 hours.
[0020] Thirdly, the present invention provides the application of polyhydroxy gemini quaternary ammonium salts for the preparation of aqueous polyurethane emulsions.
[0021] Furthermore, the specific steps for preparing the waterborne polyurethane emulsion are as follows:
[0022] Step 1: Mix the dehydrated polyol, diisocyanate and polyhydroxy gemini quaternary ammonium salt dissolved in a certain amount of solvent, and react to obtain an isocyanate-terminated intermediate.
[0023] Step 2: After the isocyanate group content reaches the theoretical value, add small molecule alkanolamine and catalyst to carry out the reaction, and then cool down after the reaction is completed.
[0024] Step 3: Deionized water is slowly added to the reaction system of Step 2 under rapid stirring and dispersed evenly to obtain the waterborne polyurethane emulsion.
[0025] Compared with the prior art, the present invention has the following advantages:
[0026] 1. The novel synthesis method of multi-hydroxyl geminal quaternary ammonium salts proposed in this invention not only produces geminal quaternary ammonium salts with multiple hydroxyl sites, enabling better incorporation into polyurethane molecular chains, but also exhibits better antibacterial properties compared to monoquaternary ammonium salts, with an inhibition rate of ≥99% against Escherichia coli and ≥98% against Staphylococcus aureus. It has broad application prospects.
[0027] 2. By quaternizing the two ends of a dihaloalcohol or dihaloalkane with a hydroxyl-containing tertiary amine, this type of polyhydroxy gemini quaternary ammonium salt contains multiple -OH sites and can be introduced into waterborne polyurethane as a hydrophilic chain extender / internal crosslinking agent. This not only imparts antibacterial properties to waterborne polyurethane but also improves the stability of waterborne polyurethane emulsions and the mechanical properties of waterborne polyurethane films.
[0028] 3. The novel synthesis method for polyhydroxy gemini quaternary ammonium salts proposed in this invention features a simple synthesis process, controllable reaction process, readily available and inexpensive raw materials, making it suitable for large-scale production. Subsequent product purification steps are relatively simple, and the purified product purity can reach over 98%. Attached Figure Description
[0029] Figure 1The 1H NMR spectrum of the dihydroxygeminid quaternary ammonium salt prepared in this invention is shown.
[0030] Figure 2 The 1H NMR spectrum of the trihydroxygeminid quaternary ammonium salt prepared in this invention is shown.
[0031] Figure 3 The photon NMR spectrum of the tetrahydroxygeminid quaternary ammonium salt prepared in this invention is shown.
[0032] Figure 4 The 1H NMR spectrum of the pentahydroxygeminid quaternary ammonium salt prepared in this invention is shown. Detailed Implementation
[0033] To further illustrate the technical solution of the present invention, the present invention will be further described below through embodiments.
[0034] Example 1
[0035] Step 1: Add 61.15g of N,N-dimethylethanolamine and 82g of anhydrous ethanol as solvents to a three-necked flask equipped with a stir bar and a condenser. Add 38.754g of 1,3-dichloropropane to a constant pressure funnel and place it in the three-necked flask.
[0036] Step 2: After heating to 75°C, slowly add 1,3-dichloropropane dropwise to carry out the quaternization reaction;
[0037] Step 3: After reacting for 8 hours, a mixed solution is obtained. After the mixed solution is cooled to room temperature, a white solid slowly precipitates out, which is the target product, Gemini quaternary ammonium salt. After the white solid has completely precipitated, the organic solvent is removed by filtration to obtain the crude product, with a yield of up to 85.2%.
[0038] Step 4: Wash the crude product several times with anhydrous ethanol, filter and dry to obtain pure dihydroxygemini quaternary ammonium salt, with a purity of up to 98.12%. The 1H NMR spectrum of dihydroxygemini quaternary ammonium salt is shown below. Figure 1 As shown.
[0039] Example 2
[0040] Step 1: Add 41.27g of N,N-dimethylethanolamine and 58g of anhydrous ethanol as solvents to a three-necked flask equipped with a stir bar and a condenser. Add 30.8g of 1,3-dichloro-2-propanol to a constant pressure funnel and place it in the three-necked flask.
[0041] Step 2: After heating to 75°C, slowly add 1,3-dichloro-2-propanol dropwise to carry out the quaternization reaction;
[0042] Step 3: After reacting for 6 hours, a mixed solution is obtained. After the mixed solution is cooled to room temperature, a white solid slowly precipitates out, which is the target product, Gemini quaternary ammonium salt. After the white solid has completely precipitated, the organic solvent is removed by filtration to obtain the crude product, with a yield of up to 92.1%.
[0043] Step 4: Wash the crude product several times with anhydrous ethanol, filter and dry to obtain pure trihydroxygemini quaternary ammonium salt, with a purity of up to 98.03%. The 1H NMR spectrum of trihydroxygemini quaternary ammonium salt is shown below. Figure 2 As shown.
[0044] Example 3
[0045] Step 1: Add 47.16g of N-methyldiethanolamine and 58g of anhydrous ethanol as solvents to a three-necked flask equipped with a stir bar and a condenser. Add 22.6g of 1,3-dichloropropane to a constant pressure funnel and place it in the three-necked flask.
[0046] Step 2: After heating to 75°C, slowly add 1,3-dichloropropane dropwise to carry out the quaternization reaction;
[0047] Step 3: After reacting for 20 hours, a mixed solution is obtained. After the mixed solution is cooled to room temperature, a white solid slowly precipitates out, which is the target product, Gemini quaternary ammonium salt. After the white solid has completely precipitated, the organic solvent is removed by filtration to obtain the crude product, with a yield of up to 75.71%.
[0048] Step 4: Wash the crude product several times with anhydrous ethanol, filter and dry to obtain pure tetrahydroxygemini quaternary ammonium salt, with a purity of up to 97.98%. The 1H NMR spectrum of tetrahydroxygemini quaternary ammonium salt is shown below. Figure 3 As shown.
[0049] Example 4
[0050] Steps: Add 41.27g of N,N-dimethylethanolamine and 53.55g of anhydrous ethanol as solvents to a three-necked flask equipped with a stir bar and a condenser. Add 29.86g of 1,3-dichloro-2-propanol to a constant pressure funnel and place it in the three-necked flask.
[0051] Step 2: After heating to 75°C, slowly add 1,3-dichloro-2-propanol dropwise to carry out the quaternization reaction;
[0052] Step 3: After reacting for 15 hours, a mixed solution is obtained. After the mixed solution is cooled to room temperature, a white solid slowly precipitates out, which is the target product, Gemini quaternary ammonium salt. After the white solid has completely precipitated, the organic solvent is removed by filtration to obtain the crude product, with a yield of up to 78.56%.
[0053] Step 4: Wash the crude product several times with anhydrous ethanol, filter and dry to obtain pure pentahydroxygemini quaternary ammonium salt, with a purity of up to 98.56%. The 1H NMR spectrum of pentahydroxygemini quaternary ammonium salt is shown below. Figure 4 As shown.
[0054] Application Example 1
[0055] Step 1: 0.02 mol of dehydrated polytetrahydrofuran ether diol (PTMG, molecular weight 1000), 0.06 mol of isoflavone diisocyanate (IPDI), and 0.0082 mol of a difunctional gemini quaternary ammonium salt dissolved in a certain amount of dimethyl sulfoxide were added to a reactor. The mixture was heated to 80°C with stirring and kept at that temperature for 4 h to obtain an isocyanate-terminated intermediate. The NCO% content was determined to be 4.6% by di-n-butylamine back titration.
[0056] Step 2: Then add 0.023 mol 1,4-butanediol chain extender and 40 ppm dibutyltin dilaurate catalyst (T-12), and react at 80 °C for 1 h. After the reaction is complete, analyze the NCO reaction by di-n-butylamine back titration and then cool down to 40 °C.
[0057] Step 3: Deionized water with a solid content of 20% is slowly added to the reaction system under rapid stirring and dispersed evenly to obtain a semi-transparent waterborne polyurethane emulsion.
[0058] Tests showed that the emulsion had a solid content of 20.12%, an average particle size of 63.69 nm, a tensile strength of 1.53 MPa at room temperature, and an elongation at break of 351.3-2.46%. It exhibited an inhibition rate of ≥99.88% against Escherichia coli and ≥98.16% against Staphylococcus aureus.
[0059] Application Example 2
[0060] Step 1: 0.02 mol of dehydrated polytetrahydrofuran ether diol (PTMG, molecular weight 1000), 0.06 mol of isoflavone diisocyanate (IPDI), and 0.0082 mol of a trifunctional gemini quaternary ammonium salt dissolved in a certain amount of dimethyl sulfoxide were added to a reactor. The mixture was heated to 80°C with stirring and kept at that temperature for 4 h to obtain an isocyanate-terminated intermediate. The NCO% content was determined to be 4.01% by di-n-butylamine back titration.
[0061] Step 2: Then add 0.023 mol 1,4-butanediol chain extender and 40 ppm dibutyltin dilaurate catalyst (T-12), and react at 80 °C for 1 h. After the reaction is complete, analyze the NCO reaction by di-n-butylamine back titration and then cool down to 40 °C.
[0062] Step 3: Deionized water with a solid content of 20% is slowly added to the reaction system under rapid stirring and dispersed evenly to obtain a semi-transparent waterborne polyurethane emulsion.
[0063] Tests showed that the emulsion had a solid content of 20.35%, an average particle size of 75.6-9.36 nm, a tensile strength of 2.56 MPa at room temperature, and an elongation at break of 346.2-3.46%. It exhibited an inhibition rate of ≥99.88% against Escherichia coli and ≥98.16% against Staphylococcus aureus.
[0064] Application Example 3
[0065] Step 1: 0.02 mol of dehydrated polytetrahydrofuran ether diol (PTMG, molecular weight 1000), 0.06 mol of isoflavone diisocyanate (IPDI), and 0.0082 mol of a 4-functional gemini quaternary ammonium salt dissolved in a certain amount of dimethyl sulfoxide were added to a reactor. The mixture was heated to 80°C with stirring and kept at that temperature for 4 h to obtain an isocyanate-terminated intermediate. The NCO% content was determined to be 3.4% by di-n-butylamine back titration.
[0066] Step 2: Then add 0.023 mol 1,4-butanediol chain extender and 40 ppm dibutyltin dilaurate catalyst (T-12), and react at 80 °C for 1 h. After the reaction is complete, analyze the NCO reaction by di-n-butylamine back titration and then cool down to 40 °C.
[0067] Step 3: Deionized water with a solid content of 20% is slowly added to the reaction system under rapid stirring and dispersed evenly to obtain a semi-transparent waterborne polyurethane emulsion.
[0068] Tests showed that the emulsion had a solid content of 20.56%, an average particle size of 83.36-36 nm, a tensile strength of 4.05 MPa at room temperature, and an elongation at break of 334.89%. It exhibited an inhibition rate of ≥99.88% against Escherichia coli and ≥98.16% against Staphylococcus aureus.
[0069] Application Example 4
[0070] Step 1: 0.02 mol of dehydrated polytetrahydrofuran ether diol (PTMG, molecular weight 1000), 0.06 mol of isoflavone diisocyanate (IPDI), and 0.0082 mol of a 5-functional gemini quaternary ammonium salt dissolved in a certain amount of dimethyl sulfoxide were added to a reactor. The mixture was heated to 80°C with stirring and kept at that temperature for 4 h to obtain an isocyanate-terminated intermediate. The NCO% content was determined to be 2.8% by di-n-butylamine back titration.
[0071] Step 2: Then add 0.023 mol 1,4-butanediol chain extender and 40 ppm dibutyltin dilaurate catalyst (T-12), and react at 80 °C for 1 h. After the reaction is complete, analyze the NCO reaction by di-n-butylamine back titration and then cool down to 40 °C.
[0072] Step 3: Deionized water with a solid content of 20% is slowly added to the reaction system under rapid stirring and dispersed evenly to obtain a semi-transparent waterborne polyurethane emulsion.
[0073] Tests showed that the emulsion had a solid content of 20.2%, an average particle size of 90.36 nm, a tensile strength of 5.27 MPa at room temperature, and an elongation at break of 320.46%. It exhibited an inhibition rate of ≥99.88% against Escherichia coli and ≥98.16% against Staphylococcus aureus.
[0074] The foregoing has shown and described the main features and advantages of the present invention. It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from its spirit or essential characteristics. Therefore, the embodiments should be considered exemplary and non-limiting in all respects, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.
[0075] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.
Claims
1. A polyhydroxy gemini quaternary ammonium salt, characterized in that, The structure is as follows: or or or ; Among them, Cl - Can be replaced with Br - or I - .
2. The method for preparing the polyhydroxy gemini quaternary ammonium salt according to claim 1, characterized in that, Includes the following steps: A hydroxyl-containing tertiary amine is quaternized with a dihaloalcohol or a dihaloalkane to obtain a polyhydroxy geminal quaternary ammonium salt. The hydroxyl-containing tertiary amine is N-methyldiethanolamine or N,N-dimethylethanolamine, the dihaloalcohol is 1,3-dichloro-2-propanol, 1,3-dibromo-2-propanol or 1,3-diiodo-2-propanol, and the dihaloalkane is 1,3-dichloropropane, 1,3-dibromopropane or 1,3-diiodopropane.
3. The method for preparing the polyhydroxy gemini quaternary ammonium salt according to claim 2, characterized in that, The preparation method is specifically as follows: A hydroxyl-containing tertiary amine is dissolved in an organic solvent and subjected to a quaternization reaction. After the reaction is completed, the organic solvent is removed to obtain a crude product. The crude product is then washed and dried to obtain the polyhydroxy gemini quaternary ammonium salt.
4. The method for preparing the polyhydroxy gemini quaternary ammonium salt according to claim 3, characterized in that, The molar ratio of the hydroxyl-containing tertiary amine to the dihaloalcohol or dihaloalkane is 1:
2.
5. The method for preparing the polyhydroxy gemini quaternary ammonium salt according to claim 3, characterized in that, The organic solvent is one of anhydrous ethanol, dimethyl sulfoxide, or ultrapure water.
6. The method for preparing the polyhydroxy gemini quaternary ammonium salt according to claim 3, characterized in that, The amount of the organic solvent used is 45% of the total material.
7. The method for preparing the polyhydroxy gemini quaternary ammonium salt according to claim 3, characterized in that, The quaternization reaction is carried out at a temperature of 60–80°C for 8–20 hours.
8. The application of the polyhydroxy gemini quaternary ammonium salt according to claim 1, characterized in that, Used to prepare waterborne polyurethane emulsions.
9. The application of the hydroxygemini quaternary ammonium salt according to claim 8, characterized in that, The specific steps for preparing the aqueous polyurethane emulsion are as follows: Step 1: Mix the dehydrated polyol, diisocyanate and polyhydroxy gemini quaternary ammonium salt dissolved in a certain amount of solvent, and react to obtain an isocyanate-terminated intermediate. Step 2: After the isocyanate group content reaches the theoretical value, add small molecule alkanolamine and catalyst to carry out the reaction, and then cool down after the reaction is completed. Step 3: Deionized water is slowly added to the reaction system of Step 2 under rapid stirring and dispersed evenly to obtain the waterborne polyurethane emulsion.