Weak-base rapidly-hydrolyzed water-based polyquaternary ammonium ester sizing agent prepared from polyester degradation product

Abstract

The invention discloses a weak-base rapidly-hydrolyzed water-based polyquaternary ammonium ester sizing agent prepared from a polyester degradation product. The preparation method comprises the following steps: adding ethylene glycol terephthalate, halogenated acetic acid and a first solvent, stirring, and removing the solvent to obtain 1, 4-benzene dicarboxylic acid and 1, 4-bis [2-[(2-chloracetyl) oxygen] ethyl ester; the preparation method comprises the following steps: adding a quaternary ammonium salt compound into a first solvent, then adding the quaternary ammonium salt compound and a di-tert-amine compound into a second solvent, stirring to obtain a product, and then precipitating and drying the weakly-alkaline rapidly-hydrolyzed waterborne polyquaternary ammonium ester sizing agent prepared from the polyester degradation product to obtain the weakly-alkaline rapidly-hydrolyzed waterborne polyquaternary ammonium ester sizing agent prepared from the polyester degradation product. The weak-base rapidly-degradable waterborne polyquaternary ammonium ester sizing agent obtained by the invention has excellent adhesive force in a spinning process with a high polyester proportion, can well bond, enhance cohesion and fit hairiness, has the advantages of stability in neutral water, weak-base degradation, quaternary ammonium salt antibiosis and the like compared with the traditional polyester sizing agent, and has a wide application prospect. The compound can also be used for disinfectants, flocculants and the like in water.

Description

Technical Field

[0001] This invention belongs to the field of polyester sizing technology, and particularly relates to a weakly alkaline, rapidly hydrolyzed, waterborne polyquaternary ester sizing agent prepared using polyester degradation products. Background Technology

[0002] Microorganisms can cause a variety of diseases, including infections, food poisoning, and infectious diseases. Antimicrobial materials can effectively prevent the growth and spread of microorganisms on surfaces or in the environment, thereby reducing the risk of infection. Traditional antimicrobial drugs based on natural or low molecular weight substances have problems such as leading to bacterial resistance, volatility, environmental pollution after sterilization, and harm to human health.

[0003] Antimicrobial polymers prepared based on the antibacterial theory of quaternary ammonium salts exhibit strong antibacterial properties. Quaternary ammonium salts typically consist of two parts: a hydrophilic portion (ammonium cation) and a hydrophobic portion (hydrophobic alkyl chains of varying lengths). Quaternary ammonium salts adsorb onto negatively charged bacteria through electrostatic interactions, hydrogen bonding, and hydrophobic interactions, creating a venting effect that inhibits bacterial growth and ultimately leads to bacterial death. Simultaneously, its hydrophobic portion can interact with the hydrophilic portion of the bacterial surface, altering its permeability and causing cell lysis and death.

[0004] There are multiple ways to degrade and recycle polyester (PET). Among them, degradation in ethylene glycol has been included in section 9.8.3 of the "Polymer Chemistry" textbook on hydrolysis, with ethylene glycol terephthalate being the main degradation product.

[0005] Currently, waterborne polyester is mainly divided into four categories: composite waterproof coatings, spinning and dissolution coatings, industrial baking coatings, and modified functional coatings. Their common advantages lie in their outstanding environmental friendliness (low VOCs, solvent-free), as well as corrosion resistance and strong adhesion. For example, composite waterproof coatings are suitable for industrial corrosion protection but are limited by low-temperature application; spinning coatings can achieve environmentally friendly fiber separation, but domestic technology still lags behind; baking coatings support low-temperature baking but have limited functionality; and silicone-modified coatings significantly improve water / heat resistance by introducing hydrophobic segments, but are more expensive. Future development focuses on environmental upgrades, multifunctional composites (such as integrated corrosion protection and wear resistance), and innovative modification technologies (such as fluorosilicone synergistic modification).

[0006] Existing polyester sizing agents have the following disadvantages: 1. Despite the introduction of water-soluble groups, their water solubility is still unsatisfactory; 2. During desizing, polyester sizing agents are very sensitive to electrolytes and will precipitate in strong electrolyte solutions. If the conditions are not properly controlled, desizing cannot be completed; 3. During desizing, alkaline solutions are used to degrade the polyester sizing agents into water-soluble acrylates, thereby achieving desizing, but these are difficult to completely dissolve in a short time.

[0007] Quaternary ammonium esters, also known as ester-based quaternary ammonium salts, are a class of cationic surfactants that link hydrophobic groups to quaternary ammonium salt end groups via ester bonds. Their chemical structure contains two long-chain alkyl ester groups. Quaternary ammonium salts (QASs) are a class of cationic compounds with simple structural compositions. The antibacterial properties of quaternary ammonium salts originate from their positively charged centers. The antibacterial mechanism is generally considered to be: the positively charged quaternary ammonium salt molecule adsorbs negatively charged bacteria under the influence of Coulomb forces; then, its alkyl chain interacts with the hydrophobic phospholipid bilayer of the cell membrane, inserting and cleaving the alkyl chain into the cell membrane, causing leakage of intracellular proteins, DNA, RNA, and other substances, leading to bacterial death. Therefore, combining quaternary ammonium salt compounds with materials can endow these materials with antibacterial properties. These antibacterial materials can be used to manufacture various products such as medical devices, food packaging, medical supplies, and household goods to reduce the growth and spread of microorganisms, helping to maintain environmental cleanliness and hygiene. The use of antibacterial materials can effectively prevent cross-infection and disease transmission, which is of great significance for protecting public health. Compared to low molecular weight QAS, polymeric QAS have a higher positive charge density, which promotes initial adsorption to the negatively charged bacterial surface and disrupts the cell membrane, thereby significantly enhancing antibacterial activity. Summary of the Invention

[0008] The purpose of this invention is to address the shortcomings of existing technologies by providing a weakly alkaline, rapidly hydrolyzed, waterborne polyquaternary ester sizing agent prepared using polyester degradation products.

[0009] The objective of this invention is achieved through the following technical solution: a weakly alkaline, rapidly hydrolyzed, aqueous polyquaternary ester sizing agent prepared using polyester degradation products, which is obtained through the following steps: (1) Ethyl terephthalate, haloacetic acid and the first solvent are stirred at 50-100℃ for 4-24 hours; after the reaction is completed, the first solvent is removed to obtain 1,4-benzenediacarboxylic acid, 1,4-bis[2-[(2-chloroacetyl)oxy]ethyl ester; the molar ratio of ethylene terephthalate and haloacetic acid is 1:2; (2) Subsequently, the 1,4-benzenediacarboxylic acid, 1,4-bis[2-[(2-chloroacetyl)oxy]ethyl ester and ditertiary amine compound prepared in step (1) are added to the second solvent and stirred at 20-70°C for 10-72 hours; the resulting product is precipitated and dried to obtain a weakly basic, rapidly hydrolyzed aqueous polyquaternary ester sizing agent prepared using polyester degradation products; the molar ratio of the 1,4-benzenediacarboxylic acid, 1,4-bis[2-[(2-chloroacetyl)oxy]ethyl ester and ditertiary amine compound is 1:1.

[0010] Further, the ditertiary amine compound is tetramethyl-1,3-propanediamine, 4,4'-methylenebis(N,N-dimethylaniline), 4,4′-(1,2-ethylenediyl)bis[N,N-dimethyl], methyl ethylamine, 4,4′-ethylethylenedi[N,N-dimethylaniline] or aniline, 4,4′-pentamethylenebis[N,N-dimethyl].

[0011] Furthermore, the first solvent is toluene, xylene, or tetrahydrofuran.

[0012] Further, the second solvent is chloroform, dichloromethane, ethyl acetate, N,N-dimethylformamide, or N,N-dimethylacetamide.

[0013] Furthermore, the haloacetic acid is chloroacetic acid, chloroacetic acid, bromoacetic acid, or iodoacetic acid.

[0014] The beneficial effects of this invention are as follows: Introducing quaternary ammonium salts into the polyester sizing system improves the water solubility of the polyester sizing, addressing the problem that ordinary polyester sizing is difficult to completely dissolve in water; furthermore, quaternary ammonium salts readily decompose under alkaline high-temperature conditions, further enhancing the rapid degradation ability of the polyester sizing under weakly alkaline conditions and improving the desizing ability of general polyester sizing during alkaline boiling. Simultaneously, the high-density quaternary ammonium salt structure ensures excellent antibacterial properties. Attached Figure Description

[0015] Figure 1 The 1H NMR spectrum of 1,4-benzenediacarboxylic acid, 1,4-bis[2-[(2-chloroacetyl)oxy]ethyl ester prepared in Example 1; Figure 2 The 1H NMR spectrum of the weakly alkaline, rapidly hydrolyzed aqueous polyquaternary ester sizing agent prepared using polyester degradation products in Example 1. Figure 3 The 1H NMR spectrum is shown for the weakly alkaline, rapidly hydrolyzed aqueous polyquaternary ester sizing agent prepared using polyester degradation products as described in Example 2. Detailed Implementation

[0016] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without inventive effort are within the scope of protection of this invention.

[0017] The principle of this invention is to first utilize an esterification reaction to react polyethylene terephthalate with chloroacetic acid to generate 1,4-benzenediacarboxylic acid, 1,4-bis[2-[(2-chloroacetyl)oxy]ethyl ester. Then, a quaternization reaction is used to react a di-tert-amine compound with 1,4-benzenediacarboxylic acid, 1,4-bis[2-[(2-chloroacetyl)oxy]ethyl ester to generate a quaternary ammonium salt polymer. After precipitation and drying, a weakly alkaline degradable polyquaternary ammonium ester sizing agent is obtained. Because the quaternary ammonium group is located ortho-positioned in the ester bond, the resulting polyquaternary ammonium ester sizing agent makes the ester bond more stable than ordinary esters under acidic or neutral conditions, yet it can rapidly hydrolyze under weakly alkaline conditions. Furthermore, this polymer contains a large number of quaternary ammonium groups, exhibiting excellent antibacterial properties.

[0018] Example 1: (1) 0.0100 mol ethylene terephthalate, 0.0200 mol chloroacetic acid and 20 ml toluene were stirred at 70 °C for 24 hours. After the reaction was completed, the toluene was removed by drying to obtain 1,4-benzenediacarboxylic acid, 1,4-bis[2-[(2-chloroacetyl)oxy]ethyl ester.

[0019] (2) Subsequently, 0.0020 mol of 1,4-benzenediacarboxylic acid and 1,4-bis[2-[(2-chloroacetyl)oxy]ethyl ester prepared in step (1) were dissolved in 4 ml of N,N-dimethylformamide and stirred at 60 °C for 48 h. The resulting product was precipitated and dried for 48 hours to obtain a weakly alkaline, rapidly hydrolyzed waterborne polyquaternary ester sizing agent prepared using polyester degradation products.

[0020] Figure 1 The 1H NMR spectrum of 1,4-benzenediacarboxylic acid, 1,4-bis[2-[(2-chloroacetyl)oxy]ethyl ester prepared in Example 1; Figure 2 The 1H NMR spectrum is shown for the weakly alkaline, rapidly hydrolyzed aqueous polyquaternary ester sizing agent prepared using polyester degradation products as described in Example 1.

[0021] Example 2: (1) 0.0100 mol ethylene terephthalate, 0.0200 mol chloroacetic acid and 20 ml toluene were stirred at 70 °C for 24 hours. After the reaction was completed, the toluene was removed by drying to obtain 1,4-benzenediacarboxylic acid, 1,4-bis[2-[(2-chloroacetyl)oxy]ethyl ester.

[0022] (2) Subsequently, 0.0020 mol of 1,4-benzenedicarboxylic acid and 1,4-bis[2-[(2-chloroacetyl)oxy]ethyl ester prepared in step (1) and 0.0020 mol of tetramethyl-1,3-propanediamine were dissolved in 4 ml of N,N-dimethylformamide and stirred at 60 °C for 48 h. The resulting product was precipitated and dried for 48 hours to obtain a weakly basic, rapidly hydrolyzed waterborne polyquaternary ester sizing agent prepared using polyester degradation products.

[0023] Figure 3 The 1H NMR spectrum is shown for the weakly alkaline, rapidly hydrolyzed aqueous polyquaternary ester sizing agent prepared using polyester degradation products as described in Example 2.

[0024] Example 3: (1) 0.0100 mol ethylene terephthalate, 0.0200 mol chloroacetic acid and 20 ml toluene were stirred at 70 °C for 24 hours. After the reaction was completed, the toluene was removed by drying to obtain 1,4-benzenediacarboxylic acid, 1,4-bis[2-[(2-chloroacetyl)oxy]ethyl ester.

[0025] (2) Subsequently, 0.0020 mol of 1,4-benzenediacarboxylic acid and 1,4-bis[2-[(2-chloroacetyl)oxy]ethyl ester prepared in step (1) were dissolved in 4 ml of chloroform with 0.0020 mol of tetramethyldiaminodiphenylmethane and stirred at 60 °C for 48 h. The resulting product was precipitated and dried for 48 hours to obtain a weakly basic, rapidly hydrolyzed waterborne polyquaternary ester sizing agent prepared using polyester degradation products.

[0026] Example 4: (1) 0.0100 mol ethylene terephthalate, 0.0200 mol chloroacetic acid and 20 ml toluene were stirred at 70 °C for 24 hours. After the reaction was completed, the toluene was removed by drying to obtain 1,4-benzenediacarboxylic acid, 1,4-bis[2-[(2-chloroacetyl)oxy]ethyl ester.

[0027] (2) Subsequently, 0.0020 mol of 1,4-benzenediacarboxylic acid and 1,4-bis[2-[(2-chloroacetyl)oxy]ethyl ester prepared in step (1) and 0.0020 mol of tetramethyl-1,3-propanediamine were dissolved in 4 ml of chloroform and stirred at 60 °C for 48 h. The resulting product was precipitated and dried for 48 hours to obtain a weakly alkaline, rapidly hydrolyzed, waterborne polyquaternary ester sizing agent prepared using polyester degradation products.

[0028] Example 5: (1) Under inert gas protection, 0.0100 mol ethylene terephthalate, 0.0200 mol chloroacetic acid and 20 ml toluene were stirred at 70 °C for 24 hours. After the reaction was completed, the toluene was removed by drying to obtain 1,4-benzenediacarboxylic acid, 1,4-bis[2-[(2-chloroacetyl)oxy]ethyl ester.

[0029] (2) Subsequently, 0.0020 mol of 1,4-benzenedicarboxylic acid and 1,4-bis[2-[(2-chloroacetyl)oxy]ethyl ester prepared in step (1) and 0.0020 mol of tetramethyl-1,3-propanediamine were dissolved in 4 ml of N,N-dimethylformamide and stirred at 60 °C for 48 h. The resulting product was precipitated and dried for 48 hours to obtain a weakly basic, rapidly hydrolyzed waterborne polyquaternary ester sizing agent prepared using polyester degradation products.

[0030] Example 6: (1) Under inert gas protection, 0.0100 mol ethylene terephthalate, 0.0200 mol chloroacetic acid and 20 ml toluene were stirred at 70 °C for 24 hours. After the reaction was completed, the toluene was removed by drying to obtain 1,4-benzenediacarboxylic acid, 1,4-bis[2-[(2-chloroacetyl)oxy]ethyl ester.

[0031] (2) Subsequently, 0.0020 mol of 1,4-benzenediacarboxylic acid and 1,4-bis[2-[(2-chloroacetyl)oxy]ethyl ester prepared in step (1) were dissolved in 4 ml of N,N-dimethylformamide and stirred at 60 °C for 48 h. The resulting product was precipitated and dried for 48 hours to obtain a weakly alkaline, rapidly hydrolyzed waterborne polyquaternary ester sizing agent prepared using polyester degradation products.

[0032] Example 7: (1) Under inert gas protection, 0.0100 mol ethylene terephthalate, 0.0200 mol chloroacetic acid and 20 ml toluene were stirred at 70 °C for 24 hours. After the reaction was completed, the toluene was removed by drying to obtain 1,4-benzenediacarboxylic acid, 1,4-bis[2-[(2-chloroacetyl)oxy]ethyl ester.

[0033] (2) Subsequently, 0.0020 mol of 1,4-benzenediacarboxylic acid and 1,4-bis[2-[(2-chloroacetyl)oxy]ethyl ester prepared in step (1) and 0.0020 mol of tetramethyl-1,3-propanediamine were dissolved in 4 ml of chloroform and stirred at 60 °C for 48 h. The resulting product was precipitated and dried for 48 hours to obtain a weakly alkaline, rapidly hydrolyzed, waterborne polyquaternary ester sizing agent prepared using polyester degradation products.

[0034] The water-soluble polyester sizing agent was prepared by following the steps in Examples 1 to 7. The gel permeation chromatography (GPC) of the polyester sizing agent was used to test its glass transition temperature, water solubility, adhesion, hygroscopicity, and the mechanical properties of the sized gauze. The testing methods are as follows: Gel permeation chromatography (GPC): Gel permeation chromatography (GPC, also known as SEC) is an instrument used to characterize the molecular weight and molecular weight distribution of polymers. Using an Agilent GPC detector, DMF (N,N-dimethylformamide) is used as the mobile phase.

[0035] Glass transition temperature (Tg): Tested using thermogravimetric analysis. A DSC analyzer from METTLER TOLEDO was used, with a heating rate of 10℃ / min, up to 140℃, to obtain the thermo-temperature profile of the product.

[0036] Water solubility: Prepare test solutions for different embodiments, weigh a certain mass of slurry or slurry film and add it to the solution to make the slurry concentration 1%, test temperature 90℃, start timing when the slurry or slurry film is added, and stop timing when the slurry is completely dissolved or hydrolyzed. Each group of samples is tested 3 times and the average value is taken as the result.

[0037] Hygroscopicity: Samples from different embodiments were dried thoroughly in an oven. Then, they were placed in a constant temperature and humidity environment for 24 hours to equilibrate, and the moisture absorption rate was obtained by weighing.

[0038] Tensile properties: The gauze was immersed in sizing solutions of different concentrations at 90°C for 5 minutes. The gauze was then cut into strips of 22*2cm and its tensile strength and elongation at break were measured using a universal testing instrument manufactured by INSTRON Instruments, Inc., USA. The tensile rate was 100mm / min. Each set of examples was tested 20 times, and the final result was the average value of the data.

[0039] The test results of the weakly alkaline, rapidly hydrolyzed waterborne polyquaternary ester sizing agents prepared using polyester degradation products obtained in Examples 1 to 7 are shown in Table 1.

[0040] Table 1: Experimental Results Data The GPC test results of the weakly alkaline rapid hydrolysis waterborne polyquaternary ester sizing agent prepared by polyester degradation product in Example 2 are shown in Table 2, including the testing of polymer number-average molecular weight (Mn), polymer weight-average molecular weight (Mp), and average value of the square of polymer molecular weight (Mz).

[0041] Table 2: GPC Test Results Data The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A weakly alkaline, rapidly hydrolyzed, aqueous polyquaternary ester sizing agent prepared using polyester degradation products, characterized in that, It is prepared through the following steps: (1) Ethyl terephthalate, haloacetic acid and the first solvent are stirred at 50-100℃ for 4-24 hours; after the reaction is completed, the first solvent is removed to obtain 1,4-benzenediacarboxylic acid, 1,4-bis[2-[(2-chloroacetyl)oxy]ethyl ester; the molar ratio of ethylene terephthalate and haloacetic acid is 1:2; (2) Subsequently, the 1,4-benzenediacarboxylic acid, 1,4-bis[2-[(2-chloroacetyl)oxy]ethyl ester and ditertiary amine compound prepared in step (1) are added to the second solvent and stirred at 20-70°C for 10-72 hours; the resulting product is precipitated and dried to obtain a weakly basic, rapidly hydrolyzed aqueous polyquaternary ester sizing agent prepared using polyester degradation products; the molar ratio of the 1,4-benzenediacarboxylic acid, 1,4-bis[2-[(2-chloroacetyl)oxy]ethyl ester and ditertiary amine compound is 1:

1.

2. The weakly alkaline, rapidly hydrolyzed, aqueous polyquaternary ammonium ester sizing agent prepared using polyester degradation products according to claim 1, characterized in that, The ditertiary amine compound is tetramethyl-1,3-propanediamine, 4,4'-methylenebis(N,N-dimethylaniline), 4,4′-(1,2-ethylenediyl)bis[N,N-dimethyl], methyl ethylamine, 4,4′-ethylethylenedi[N,N-dimethylaniline] or aniline, or 4,4′-pentamethylenebis[N,N-dimethyl].

3. The weakly alkaline, rapidly hydrolyzed, aqueous polyquaternary ammonium ester sizing agent prepared using polyester degradation products according to claim 1, characterized in that, The first solvent is toluene, xylene, or tetrahydrofuran.

4. The weakly alkaline, rapidly hydrolyzed, aqueous polyquaternary ammonium ester sizing agent prepared using polyester degradation products according to claim 1, characterized in that, The second solvent is chloroform, dichloromethane, ethyl acetate, N,N-dimethylformamide, or N,N-dimethylacetamide.

5. The weakly alkaline, rapidly hydrolyzed, aqueous polyquaternary ammonium ester sizing agent prepared using polyester degradation products according to claim 1, characterized in that, The haloacetic acid is chloroacetic acid, chloroacetic acid, bromoacetic acid, or iodoacetic acid.

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