Preparation method of washable antistatic agent of macromolecular quaternary ammonium salt

Abstract

The invention relates to the field of textile assistants, and discloses a preparation method of a washable antistatic agent of macromolecular quaternary ammonium salt, which comprises the following steps: esterifying cardanol polyoxyethylene ether, maleic anhydride and dimethylaminoethanol step by step, then adding benzyl chloride for quaternization reaction to obtain cardanol polyoxyethylene ether maleic acid ethyl dimethyl benzyl ammonium chloride, and then adding benzyl chloride for quaternization reaction to obtain the washable antistatic agent of macromolecular quaternary ammonium salt. And by utilizing the emulsifying property and reactivity of the copolymer, styrene (ST) and allyl polyoxyethylene polyoxypropylene ether are used as comonomers, azobis (isobutylamidine hydrochloride) (AIBA) is used as an initiator, and the polymer quaternary ammonium salt type antistatic agent is obtained in an emulsion polymerization manner. The high-molecular quaternary ammonium salt washable antistatic agent prepared by the invention can effectively solve the problem of static electricity on the surface of a fabric caused in actual production, can also solve the problem of insufficient washability of a conventional antistatic agent, can still keep the antistatic performance of the surface of the fabric after being washed with water for 10-15 times, and is a washable antistatic agent.

Description

Technical Field

[0001] The invention relates to the field of textile auxiliaries, in particular to a method for preparing a washable antistatic agent of a polymer quaternary ammonium salt. Background Art

[0002] Due to the poor hygroscopicity of polyester fibers, fabrics are susceptible to high temperatures, dry environments, and triboelectric charging during production and processing, which can easily attract airborne dust and contaminate the fabric. Furthermore, high static electricity on the fabric surface can cause safety accidents. Furthermore, static electricity generated when worn can still cause discomfort and seriously affect wearability. All of these factors place high demands on the fabric's antistatic properties. Traditional antistatic agents are primarily composed of small-molecule surfactants. The hydrophilic groups of surfactants promote moisture absorption on the fabric surface, thereby dissipating static charge and achieving an antistatic effect. However, surfactants have limited adsorption fastness on fabric surfaces, often significantly degrading their performance after washing. Therefore, an antistatic agent with excellent washability is urgently needed for fabric finishing. Summary of the Invention

[0003] The technical problem to be solved by the present invention is to overcome the defects of the above-mentioned prior art and provide a method for preparing a washable antistatic agent of a polymer quaternary ammonium salt.

[0004] In order to achieve the above object, the present invention adopts the following technical solutions: A: Add 90-110 parts of cardanol polyoxyethylene ether and 10-11 parts of maleic anhydride to a reaction vessel, heating and stirring. When the temperature reaches 95-105°C, add 1-3 parts of p-toluenesulfonic acid and keep warm for 2-4 hours to obtain the product, maleic anhydride half ester. Then add 11-12 parts of dimethylaminoethanol and react under a vacuum of -0.08 to -0.1 MPa for 2-4 hours to completely esterify the maleic anhydride half ester. Adjust the pH to 10-11 with liquid caustic soda, then add 10-12 parts of benzyl chloride and continue the reaction for 3-5 hours to obtain cardanol polyoxyethylene ether maleic acid ethyl dimethylbenzyl ammonium chloride. Its general structure is shown below:

[0005] Where 0≤a≤3; n=8~12 B: Mix 60-70 parts of cardanol polyoxyethylene ether maleic acid ethyl dimethyl benzyl ammonium chloride, 5-7 parts of fatty alcohol polyoxyethylene ether, 10-11 parts of styrene, 40-60 parts of allyl polyoxyethylene polyoxypropylene ether, and 400-500 parts of deionized water. Pre-emulsify in a disperser to obtain a pre-emulsion. Add the pre-emulsion to a reaction vessel equipped with a condenser reflux device, start stirring, add glacial acetic acid (98%) to adjust the pH to 5-6, and heat to 80-90°C. Dissolve 0.3-0.5 parts of azobisisobutylamidine hydrochloride in 45-55 parts of deionized water and slowly add it dropwise to the reaction vessel using a peristaltic pump. Continue the addition for 2-4 hours. After completion, keep the mixture warm for 1-3 hours. The emulsion product can be used as a high-molecular-weight quaternary ammonium salt-based washable antistatic agent. Its general structural formula is shown below:

[0006] Where 0≤a≤3; n=8~12; Due to the application of the above technical solution, the present invention has the following advantages: Cardanol polyoxyethylene ether maleate ethyl dimethyl benzyl ammonium chloride was prepared in advance as a reactive cationic surfactant based on demand. Its structure contains benzene rings, long-chain alkyl groups, and hydrophilic segments, but its washability is slightly insufficient. Leveraging its combined emulsifying and reactive properties, a high-molecular-weight random copolymer with styrene and allyl polyoxyethylene polyoxypropylene ether was prepared to create a washable antistatic agent.

[0007] The presence of cationic groups of polyoxyethylene ether and quaternary ammonium salts in this polymer structure can absorb moisture from the air and promote charge transfer, resulting in excellent antistatic properties. Allyl polyoxyethylene polyoxypropylene ether contains polyoxyethylene ether and polyoxypropylene ether, with polyoxypropylene ether as the end group to achieve a balance between hydrophilicity and washability.

[0008] At the same time, there are a large number of benzene ring structures in the polymer structure. Some of the benzene rings can form a eutectic structure with the benzene rings in the polyester fiber during high-temperature heat setting, and are embedded in the fiber surface to achieve a wash-resistant effect; the remaining benzene rings can also be arranged in an orderly manner on the fiber surface during high-temperature heat setting to form a strong film, effectively improving the wash resistance. DETAILED DESCRIPTION

[0009] The present invention will be further described below through specific embodiments. Example

[0010] 100 kg of cardanol polyoxyethylene ether (CPEO-10) and 10 kg of maleic anhydride were added to a reaction vessel in a proportioned manner by mass. The temperature was raised and stirred. When the temperature reached 105°C, 1.5 kg of p-toluenesulfonic acid was added and the temperature was kept for 3 h to obtain the product, maleic anhydride half ester. 11 kg of dimethylaminoethanol was then added, and the reaction was carried out under a vacuum degree of -0.09 MPa for 3 h to completely esterify the maleic anhydride half ester. After adjusting the pH to 11 with liquid caustic soda, 11 kg of benzyl chloride was added, and the reaction was continued for 4 h to obtain cardanol polyoxyethylene ether maleic acid ethyl dimethylbenzyl ammonium chloride (CPEO-1027).

[0011] 65 kg CPEO-1027, 7 kg fatty alcohol polyoxyethylene ether (AEO-9), 10.5 kg styrene, 50 kg allyl polyoxyethylene (3) polyoxypropylene ether (6), and 450 kg deionized water were mixed and stirred in a disperser for 45 min to obtain a pre-emulsion. The pre-emulsion was added to a reaction vessel equipped with a condensation reflux device, and stirring was started. The temperature was raised to 85 °C and the pH was adjusted to 5-6 by glacial acetic acid (98%). 0.4 kg azobisisobutylamidine hydrochloride was dissolved in 50 kg deionized water and slowly added dropwise to the reaction vessel by a peristaltic pump. The addition time was continued for 3 h. After the addition was completed, the temperature was kept warm for 2 h. The emulsion product can be used as a polymer quaternary ammonium salt type antistatic agent. Example

[0012] 90 kg of cardanol polyoxyethylene ether (CPEO-8) and 10 kg of maleic anhydride were added to a reaction vessel in a proportioned manner by mass. The temperature was raised and stirred. When the temperature reached 100°C, 1 kg of p-toluenesulfonic acid was added and the temperature was kept for 3 h to obtain the product, maleic anhydride half ester. 12 kg of dimethylaminoethanol was then added and the reaction was carried out under a vacuum degree of -0.08 MPa for 3 h to completely esterify the maleic anhydride half ester. The pH was adjusted to 10.5 with liquid caustic soda, and 10 kg of benzyl chloride was added. The reaction was continued for 4 h to obtain cardanol polyoxyethylene ether maleic acid ethyl dimethylbenzyl ammonium chloride (CPEO-827).

[0013] 60 kg of CPEO-827, 6 kg of fatty alcohol polyoxyethylene ether (AEO-9), 10.5 kg of styrene, 60 kg of allyl polyoxyethylene (4) polyoxypropylene ether (7), and 470 kg of deionized water were mixed and stirred thoroughly in a disperser for 50 min to obtain a pre-emulsion. The pre-emulsion was added to a reaction vessel equipped with a condensation reflux device, and stirring was started. The temperature was raised to 80 °C and glacial acetic acid (98%) was added to adjust the pH to 5-6. 0.5 kg of azobisisobutylamidine hydrochloride was dissolved in 50 kg of deionized water and slowly added to the reaction vessel through a peristaltic pump. The addition time was continued for 3 hours. After the addition was completed, the temperature was kept warm for 2 hours. The emulsion product can be used as a polymer quaternary ammonium salt type antistatic agent. Example

[0014] 110 kg of cardanol polyoxyethylene ether (CPEO-12) and 11 kg of maleic anhydride were added to a reaction vessel in proportion by mass. The temperature was raised and stirred. When the temperature reached 105°C, 2 kg of p-toluenesulfonic acid was added and the temperature was kept for 3 h to obtain the product, maleic anhydride half ester. 12 kg of dimethylaminoethanol was then added and the reaction was carried out under a vacuum of -0.1 MPa for 3 h to completely esterify the maleic anhydride half ester. After adjusting the pH to 10 with liquid caustic soda, 12 kg of benzyl chloride was added and the reaction was continued for 4 h to obtain cardanol polyoxyethylene ether maleic acid ethyl dimethylbenzyl ammonium chloride (CPEO-1227).

[0015] 70 kg of CPEO-1227, 5 kg of fatty alcohol polyoxyethylene ether (AEO-9), 10.5 kg of styrene, 40 kg of allyl polyoxyethylene (2) polyoxypropylene ether (5), and 430 kg of deionized water were mixed and stirred thoroughly in a disperser for 30 minutes to obtain a pre-emulsion. The pre-emulsion was added to a reaction vessel equipped with a condensation reflux device, and stirring was started. The temperature was raised to 90 °C and glacial acetic acid (98%) was added to adjust the pH to 5-6. 0.4 kg of azobisisobutylamidine hydrochloride was dissolved in 50 kg of deionized water and slowly added to the reaction vessel through a peristaltic pump. The addition time was continued for 3 hours. After the addition was completed, the temperature was kept at room temperature for 2 hours. The emulsion product can be used as a polymer quaternary ammonium salt type antistatic agent.

[0016] Application evaluation process: Test standard: GB / T 12703.1~2021 Experimental samples: Example 1, Example 2, Example 3, conventional antistatic agent, market standard Experimental fabric: White flannel Experimental equipment: M~6 small padder, continuous setting dryer PT~1A, YG(B)342E fabric induction static tester, standard drum washing machine Experimental methods and steps: Dosage: 10g / L Padding method: dip and pad the working solution → 190℃×90s setting → test the antistatic performance after placement Test results: 1. Electrostatic half-life (unit: s)

[0017] From the above test results, it is not difficult to see that conventional antistatic agents composed of small molecule surfactants have excellent initial performance but lack wash resistance. The market standard sample has a wash resistance of about 5 times, and the antistatic agent samples in the examples have a strong water wash resistance of 10 to 15 times.

[0018] 2. Fabric surface peak voltage (unit: V)

[0019] From the above test results, unlike the electrostatic half-life, the electrostatic voltage performance changes more significantly with the increase in the number of water washings. The performance of the antistatic agent sample in the embodiment after water washing is also better than that of conventional small molecule antistatic agents and market standards.

[0020] The technical scope of the present invention is not limited to the contents of the above description. Those skilled in the art can make various deformations and modifications to the above embodiments without departing from the technical concept of the present invention, and these deformations and modifications should all fall within the scope of the present invention.

Claims

1. A method for preparing a washable antistatic agent of a polymer quaternary ammonium salt, characterized in that The steps include: A: Add 90-110 parts of cardanol polyoxyethylene ether and 10-11 parts of maleic anhydride to a reaction vessel in proportion by mass, start heating and stirring, and when the temperature rises to 95-105°C, add 1-3 parts of p-toluenesulfonic acid and keep warm for 2-4 hours to obtain the product of maleic anhydride half ester; then add 11-12 parts of dimethylaminoethanol and react under a vacuum degree of -0.08 to -0.1 MPa for 2-4 hours to completely esterify the maleic anhydride half ester; adjust the pH to 10-11 with liquid alkali (32% NaOH aqueous solution), then add 10-12 parts of benzyl chloride and continue the reaction for 3-5 hours to obtain cardanol polyoxyethylene ether maleic acid ethyl dimethylbenzyl ammonium chloride; B: Mix 60-70 parts of cardanol polyoxyethylene ether maleic acid ethyl dimethyl benzyl ammonium chloride, 5-7 parts of fatty alcohol polyoxyethylene ether, 10-11 parts of styrene, 40-60 parts of allyl polyoxyethylene polyoxypropylene ether, and 400-500 parts of deionized water. Pre-emulsify in a disperser to obtain a pre-emulsion. Add the pre-emulsion to a reaction vessel equipped with a condenser reflux device, start stirring, add glacial acetic acid (98%) to adjust the pH to 5-6, and heat to 80-90°C. Dissolve 0.3-0.5 parts of azobisisobutylamidine hydrochloride in 45-55 parts of deionized water and slowly add it dropwise to the reaction vessel using a peristaltic pump for 2-4 hours. After the addition is complete, keep the mixture warm for 1-3 hours. The emulsion product can be used as a washable antistatic agent for a high molecular weight quaternary ammonium salt.

2. The method for preparing a wash-resistant antistatic agent of a polymeric quaternary ammonium salt according to claim 1, wherein: The number of ethylene oxide (~CH2CH2O~) segments in the structure of the cardanol polyoxyethylene ether maleic acid ethyl dimethyl benzyl ammonium chloride is 8 to 12; The allyl polyoxyethylene polyoxypropylene ether contains 2 to 4 oxyethylene (~CH2CH2O~) segments and 5 to 7 oxypropylene (~CH(CH3)CH2O~) segments, and the polyoxypropylene ether serves as the terminal group.

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