Anti-wicking polyester yarn oiling agent as well as synthesis method, composition and application thereof

Abstract

The invention belongs to the technical field of anti-wicking polyester yarns, and particularly relates to an anti-wicking polyester yarn oiling agent as well as a synthesis method, a composition and application thereof. The structural formula of the anti-wicking polyester yarn oiling agent is R-SO2-CH2COOH, wherein R is a perfluoro substituted alkyl group or a partially fluoro substituted alkyl group. The anti-wicking polyester yarn oiling agent is used as a solution preparation of a fluorocarbon anti-wicking agent, the oiling agent, a silicone wax anti-wicking agent and a basic spinning oil agent are prepared into an oiling composition, and after the oiling composition is used for polyester industrial yarn emulsion coating and heating to prepare a finished product, the wicking height of the anti-wicking polyester yarn is remarkably reduced, the fiber strength and the like are not affected, and the anti-wicking polyester yarn has good anti-wicking performance. And the method is suitable for industrial application.

Description

Technical Field

[0001] The present invention belongs to the technical field of anti-wicking polyester filaments, and particularly relates to an oiling agent for anti-wicking polyester filaments, a synthesis method, a composition and uses thereof. Background Art

[0002] Anti-wicking polyester filaments, namely anti-wicking polyester industrial filaments, also known as anti-wicking polyester industrial filaments, etc., are artificial fibers suitable for materials such as advertising light box cloth, truck tarpaulins, and pool cloth. Its function is to prevent rainwater, etc. from infiltrating into the fibers along the yarns and migrating along the fibers, resulting in mildew spots and deterioration of fiber properties. The anti-wicking performance of anti-wicking polyester filaments depends on the anti-wicking agent coated on their surfaces, such as fluorocarbon anti-wicking agents, silicone wax anti-wicking agents, etc., that is, the anti-wicking agent is used to endow the polyester industrial filaments with waterproof, oil-proof and low wetting properties (see patent document CN201610781457.X). All or part of the hydrogen atoms in the hydrocarbon chain of the fluorocarbon anti-wicking agent are replaced by fluorine atoms.

[0003] Currently, research is also being conducted on fluorine-free normal alkane anti-wicking agents, but such anti-wicking agents have poor crystallization properties and require normal alkanes with no less than 16 carbon atoms (such as octadecyl acrylate) to achieve a better fiber coating effect. Such anti-wicking agents have not yet achieved the anti-wicking effect of fluorocarbon anti-wicking agents.

[0004] The anti-wicking performance (wicking height) is one of the key indicators for inspecting anti-wicking polyester filaments. The China Chemical Fiber Industry Association standard T / CCFA01035-2018 gives the methods and standards for testing the wicking height of anti-wicking polyester industrial filaments. For example, a wicking height below 5 mm is a first-class product, 5 mm to 20 mm is a second-class product, and 20 mm to 50 mm is a qualified product. However, foreign customers have relatively high requirements for the anti-wicking performance of products.

[0005] The preparation of anti-wicking polyester filaments generally includes processes such as polyester chips, pre-crystallization, pre-heating, solid-phase polycondensation, screw melting extrusion, spinning box, metering pump, spinning pack, post-heating zone, cooling and shaping, oiling, pre-network, draw-texturing hot roller, netter, winding and bobbin dropping, inspection and packaging, etc. Among them, the anti-wicking agent is usually added to the anti-wicking oil agent for oiling, and the preparation of the anti-wicking oil agent is difficult and generally an emulsion is prepared for use.

[0006] The level and stability of the anti-wicking performance of anti-wicking polyester filaments are one of the common technical problems in this field. To improve its anti-wicking performance, the currently discovered problem causes and solutions mainly include:

[0007] Problems of polyester industrial yarn itself: That is, the uniformity of polyester industrial yarn itself and the like have an impact on the coating of the anti-wicking agent and the anti-wicking performance. Therefore, some researchers modified the polyester industrial yarn itself by introducing branched chains to increase the spatial interval, thereby improving the anti-wicking performance of the polyester industrial yarn (see patent document CN201610781457.X).

[0008] Problems of the anti-wicking agent itself: That is, the combination and ratio of the anti-wicking agent and the like have an impact on the coating of the anti-wicking agent and the anti-wicking performance. Therefore, some researchers improved the anti-wicking performance of polyester industrial yarn by adjusting the ratio and combination of fluorocarbon anti-wicking agents and silicone wax anti-wicking agents (see patent documents CN202210455780.3 and CN202311564927.3).

[0009] Problems of the oil agent and oiling rate of the anti-wicking agent: That is, the precipitation of the oil agent emulsion will block the pipeline, resulting in uneven oiling. If the oiling rate is too high, the spinning condition will be unstable, and if it is too low, it is difficult to ensure the anti-wicking effect. Therefore, some researchers improved the anti-wicking performance of polyester industrial yarn by improving the formula of the spinning oil agent and controlling the oiling process, such as controlling the oil agent suspension and inspecting the pipeline (see the literature "Discussion on the production process of a high-strength anti-wicking polyester industrial yarn" published by Liu Shusheng et al. in the Polyester Industry Magazine in 2023; CN201510217024.7).

[0010] However, the anti-wicking performance of polyester industrial yarn still needs to be further improved to adapt to the complex application scenarios faced by fabrics. Summary of the Invention

[0011] In view of the above technical problems, the object of the present invention is to provide an anti-wicking agent for oiling polyester filaments, a synthesis method, a composition and a use thereof. That is, the present invention provides a chemical reagent and its synthesis method for an anti-wicking agent coating (oiling) process for polyester industrial yarn, a composition containing the anti-wicking agent for oiling polyester filaments, and its use.

[0012] The technical solution adopted by the present invention is as follows:

[0013] First of all, the present invention provides an anti-wicking agent for oiling polyester filaments, that is, a chemical substance for an anti-wicking agent coating (oiling) process for polyester industrial yarn, which can be used as an emulsifier for fluorocarbon anti-wicking agents. The structural formula of the anti-wicking agent for oiling polyester filaments is: R-SO 2 -CH 2 COOH, where R is a perfluoro-substituted alkyl or a partially fluorinated alkyl.

[0014] Preferably, the perfluoro-substituted alkyl is selected from any one of perfluorohexyl and perfluorooctyl; the partially fluorinated alkyl is selected from any one of perfluorohexylethyl and perfluorooctylethyl.

[0015] Secondly, the present invention also provides a method for synthesizing the above-mentioned sizing agent for anti-wicking polyester filaments, which comprises the following steps:

[0016] S1: In an aqueous system, sodium metabisulfite, sodium hydroxide, perfluoroalkylsulfonyl chloride or partially fluorinated alkylsulfonyl chloride are added, and a reaction occurs to generate sodium perfluoroalkylsulfinate or sodium partially fluorinated alkylsulfinate; after the reaction is completed, water is removed, and ethanol is added to prepare an ethanol solution of sodium perfluoroalkylsulfinate or sodium partially fluorinated alkylsulfinate;

[0017] S2: Prepare a chloroacetic acid-ethanol solution, mix it with the ethanol solution of sodium perfluoroalkylsulfinate or sodium partially fluorinated alkylsulfinate obtained in step S1, and react to generate the sizing agent for anti-wicking polyester filaments.

[0018] According to its reaction principle, its reaction formula is shown as formula I below, reaction formula I:

[0019]

[0020] Preferably, the synthesis method further comprises the following steps:

[0021] S3: After the reaction in step S2 is completed, the reaction system is filtered, and the filtrate is dried to remove the solvent to obtain the sizing agent for anti-wicking polyester filaments.

[0022] More preferably, in reaction formula I, R is perfluorohexyl. In step S1, the weight ratio of the feeding amounts of water, sodium metabisulfite, sodium hydroxide, perfluoroalkylsulfonyl chloride, and ethanol is 5:1.5:0.4:0.75:10, and the reaction temperature is about 60°C; when preparing the chloroacetic acid-ethanol solution in step S2, the weight ratio of the feeding amounts of chloroacetic acid and ethanol is 1:1, and the reaction temperature is 55°C.

[0023] More preferably, in reaction formula I, R is perfluorohexylethyl. In step S1, the weight ratio of the feeding amounts of water, sodium metabisulfite, sodium hydroxide, partially fluorinated alkylsulfonyl chloride, and ethanol is 5:1.5:0.4:0.8:10, and the reaction temperature is about 60°C; when preparing the chloroacetic acid-ethanol solution in step S2, the weight ratio of the feeding amounts of chloroacetic acid and ethanol is 1:1, and the reaction temperature is 55°C.

[0024] More preferably, in reaction formula I, R is perfluorooctyl. In step S1, the weight ratio of the feeding amounts of water, sodium metabisulfite, sodium hydroxide, perfluoroalkylsulfonyl chloride, and ethanol is 5:1.5:0.4:1:10, and the reaction temperature is about 60°C; when preparing the chloroacetic acid-ethanol solution in step S2, the weight ratio of the feeding amounts of chloroacetic acid and ethanol is 1:1, and the reaction temperature is 55°C.

[0025] Further preferably, in Reaction Formula I, R is perfluorooctylethyl. In Step S1, the weight ratio of water, sodium metabisulfite, sodium hydroxide, perfluoroalkylsulfonyl chloride, and ethanol in the feeding amounts is 5:1.5:0.4:1:10, and the reaction temperature is about 60°C. When preparing the chloroacetic acid-ethanol solution in Step S2, the weight ratio of chloroacetic acid to ethanol in the feeding amounts is 1:1, and the reaction temperature is 55°C.

[0026] In addition, the present invention also provides a sizing composition for anti-wicking polyester filaments. The sizing composition is made from a fluorocarbon anti-wicking agent solution, a silicone wax anti-wicking agent, and a spinning finish. The fluorocarbon anti-wicking agent solution contains a fluorocarbon monomer and an emulsifier. The structural formula of the emulsifier is: R-SO 2 -CH 2 COOH, where R is a perfluoroalkyl group or a partially fluorinated alkyl group.

[0027] Preferably, the fluorocarbon anti-wicking agent solution is made from an emulsifier, a fluorocarbon monomer, a long-chain alkyl monomer, an auxiliary monomer, and deionized water. The fluorocarbon monomer is perfluorohexylethyl acrylate, the long-chain alkyl monomer is octadecyl methacrylate, and the auxiliary monomer is methyl methacrylate.

[0028] Further preferably, the weight ratio of the emulsifier, the fluorocarbon monomer, the long-chain alkyl monomer, the auxiliary monomer, and deionized water in the feeding amounts is 3:10:5:2:80.

[0029] Further preferably, the weight ratio of the fluorocarbon anti-wicking agent solution, the silicone wax anti-wicking agent, and the spinning finish in the feeding amounts is 30:5:65.

[0030] In addition, the present invention also provides the use of the sizing agent for anti-wicking polyester filaments or the sizing composition for anti-wicking polyester filaments as described above in sizing anti-wicking agents for polyester industrial filaments.

[0031] The sizing agent and composition for anti-wicking polyester filaments of the present invention have the following advantages:

[0032] The sizing agent for anti-wicking polyester filaments of the present invention can be used as a solution formulation of a fluorocarbon-based anti-wicking agent, i.e., an emulsifier for a fluorocarbon-based anti-wicking agent solution. It is formulated with a fluorocarbon-based anti-wicking agent into a solution, and then formulated with a silicone wax anti-wicking agent and a basic spinning finish into a sizing composition for use in emulsion coating of polyester filaments, which can significantly reduce the wicking height of anti-wicking polyester filaments, and the breaking strength of the yarn, the size of the emulsion particles, etc. are not affected. Through comparative analysis of the experimental results, its significant reduction in wicking height is related to -SO 2 -CH 2The decarboxylation of the COOH group is related to the influence on the sizing composition. The industrial spinning temperature is relatively high, generally around 240 - 275 °C, and the heat setting process temperature is sufficient to cause the decarboxylation of the -SO 2 -CH 2 COOH group, and the fluorine-containing group can continue to play the role of anti-wicking. Therefore, the effect corresponding to the technical solution of the sizing agent for anti-wicking polyester filaments depends on the -SO 2 -CH 2 COOH group of the sizing agent for anti-wicking polyester filaments. Therefore, the sizing agent for anti-wicking polyester filaments is applicable to other cases where R is a perfluoro-substituted alkyl group or a partially fluorinated alkyl group. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 Infrared spectrum of perfluorohexylethylsulfonylacetic acid;

[0034] Figure 2 Infrared spectrum of perfluorooctylsulfonylacetic acid. DETAILED DESCRIPTION OF THE INVENTION

[0035] The present invention will be further described below in conjunction with specific embodiments. It should be understood that the specific embodiments are only used to explain the present invention and are not used to limit the protection scope of the present invention. When referring to the reaction feed ratio or formulation ratio in the following embodiments, the same measurement standard is used for the weight parts in the same embodiment. For example, in Example 1, each weight part can be regarded as the same measurement unit such as 1 kg or 1 g.

[0036] The present invention uses infrared spectroscopy, fluorine spectroscopy and / or liquid chromatography - mass spectrometry to analyze the synthesized products, and the liquid chromatography - mass spectrometry can give the retention time and molecular weight information of the substances. The liquid chromatography - mass spectrometry used is Waters ACQUITY H Class liquid system and SDQ2 single quadrupole mass spectrometer.

[0037] Chromatography system:

[0038] Chromatographic column: C18 column (1.6 μm, 2.1 * 150 mm); column temperature: 40 °C; sample chamber temperature: 10 °C; injection volume: 2 μL; solvent: methanol, sample concentration: 2000 ppm; flow rate: 0.3 mL / min; mobile phase A: 0.1% acetic acid aqueous solution; mobile phase B: 0.1% acetic acid methanol solution; gradient elution program is shown in Table 1.

[0039] Table 1 Mobile phase gradient elution program

[0040] Time(min) A％ B％ 0 90 10 1 90 10 11 5 95 14 5 95 14.5 90 10 17 90 10

[0041] Mass spectrometry system:

[0042] Ionization method: ESI - ; Mode: SIR; Ion source temperature: 150℃; Cone voltage: 55V.

[0043] Example 1: Perfluorohexylethylsulfonylacetic acid, an anti-wicking polyester yarn oiling agent, and a synthesis method

[0044] The structural formula of the anti-wicking polyester yarn oiling agent is:

[0045] C 6 F 13 -CH(-CH 3 )-SO 2 -CH 2 COOH (perfluorohexylethylsulfonylacetic acid, R is a partially fluorinated alkyl group)

[0046] The synthesis method is:

[0047] In an enameled reactor, add 5 parts by weight of water, 1.5 parts by weight of sodium metabisulfite and 0.4 parts by weight of sodium hydroxide. After sufficient stirring, control the reaction temperature to 60°C, add 0.8 parts by weight of perfluorohexylethylsulfonyl chloride dropwise, react for 2 hours, heat to 105°C and distill under reduced pressure to remove water. After the water is completely removed, cool to room temperature, add 10 parts by weight of ethanol into the reactor, stir to dissolve, press into a filter kettle to filter, remove the white solid sodium salt, and press the filtrate into another enameled reactor with an air compressor.

[0048] Dissolve 0.5 parts by weight of chloroacetic acid in 0.5 parts by weight of ethanol, add the chloroacetic acid-ethanol solution to the sodium perfluorohexyl ethyl sulfinate-ethanol solution at room temperature, raise the temperature to 55°C, react for 2 hours, press into a filter kettle for filtration to remove white solid sodium chloride, and pump the filtrate into a closed organic solvent spray dryer to obtain the product, white solid perfluorohexyl ethyl sulfonylacetic acid, with a yield of 91.95%.

[0049] Under the aforementioned HPLC-MS test conditions, the retention time of perfluorohexylethylsulfonylacetic acid is 9.42 min, and m / z is 469.02, which is the MH quasi-molecular ion peak of perfluorohexylethylsulfonylacetic acid. The infrared spectrum of perfluorohexylethylsulfonylacetic acid is shown in Figure 1 . 3400~3000cm in the figure -1 The broad peak at 2973cm is the OH stretching vibration peak of the carboxyl group; -1 CH 3 Antisymmetric stretching vibration peak; 2927cm -1 The stretching vibration peak of CH 2 Antisymmetric stretching vibration peak; 2849cm -1 CH 2 Symmetric stretching vibration peak; 1761cm -1The C=O stretching vibration absorption peak of the carbonyl group in carboxylic acid is at 1340 cm -1 The peak of sulfonyl antisymmetric stretching vibration is at 1199cm -1 CF 3 CF 2 Antisymmetric stretching vibration peak; 1148cm -1 CF 3 Symmetric stretching vibration peak; 1126cm -1 The CF2 symmetric stretching vibration peak is at 916cm -1 The C-OH out-of-plane bending vibration peak of the carboxyl group is at 642 cm -1 CF 3 CF 2 Variable angle vibration peak. NMR of perfluorohexylethylsulfonylacetic acid: 19 F NMR (400MHz, CDCl 3 ): δ (ppm) -80.72 (s, 3F), -121.01 (s, 2F), -121.73 (s, 2F), -122.66 (s, 2F), -123.48 (s, 2F), -126.07 (s, 2F)

[0050] Example 2: Perfluorooctane sulfonylacetic acid, an anti-wicking polyester yarn oiling agent, and its synthesis method

[0051] The structural formula of the anti-wicking polyester yarn oiling agent is:

[0052] C 8 F 17 -SO 2 -CH 2 COOH (perfluorooctanesulfonylacetic acid, R is a perfluoroalkyl group)

[0053] The synthesis method is:

[0054] In an enameled reactor, add 5 parts by weight of water, 1.5 parts by weight of sodium metabisulfite and 0.4 parts by weight of sodium hydroxide. After sufficient stirring, control the reaction temperature to about 60°C, add 1 part by weight of perfluorooctane sulfonyl chloride dropwise, react for 2 hours, heat to 105°C and remove water by vacuum distillation. After the water is completely removed, cool to room temperature, add 10 parts by weight of ethanol into the reactor, stir to dissolve, press into a filter kettle to filter, remove the white solid sodium salt, and press the filtrate into another enameled reactor with an air compressor.

[0055] Dissolve 0.5 parts by weight of chloroacetic acid in 0.5 parts by weight of ethanol, add the chloroacetic acid-ethanol solution to the sodium perfluorooctane sulfinate-ethanol solution at room temperature, raise the temperature to 55°C, react for 2 hours, press into a filter kettle for filtration to remove white solid sodium chloride, and pump the filtrate into a closed organic solvent spray dryer to obtain solid perfluorooctane sulfonyl acetic acid as a product, with a yield of 94.96%.

[0056] Under the test conditions of the above liquid chromatography - mass spectrometry, the retention time of perfluorooctanesulfonyl acetic acid is 7.14 min, m / z = 540.84, which is the M - H quasi - molecular ion peak of perfluorooctanesulfonyl acetic acid. The infrared spectrum of perfluorooctanesulfonyl acetic acid is shown in Figure 2 . In the figure, the broad peak at 3700 - 3000 cm -1 is the O - H stretching vibration peak of the carboxyl group; the peak at 2920 cm -1 is the asymmetric stretching vibration peak of CH 2 ; the peak at 2852 cm -1 is the symmetric stretching vibration peak of CH 2 ; the peak at 1786 cm -1 is the C = O stretching vibration absorption peak of the carbonyl group in the carboxylic acid; the peak at 1347 cm -1 is the asymmetric stretching vibration peak of the sulfonyl group; the peak at 1259 cm -1 is the asymmetric stretching vibration peak of CF 3 ; the peak at 1197 cm -1 is the asymmetric stretching vibration peak of CF 2 ; the peak at 1130 cm -1 is the symmetric stretching vibration peak of CF 2 ; the peak at 917 cm -1 is the out - of - plane bending vibration peak of C - OH in the carboxyl group; the peak at 642 cm -1 is the deformation vibration peak of CF 3 , CF 2 . The NMR of perfluorooctanesulfonyl acetic acid: 19 F NMR(400 MHz, CDCl 3 ): δ(ppm) - 59.18(s, 2F), - 80.95(s, 3F), - 113.16(s, 2F), - 121.00(s, 2F), - 121.99(s, 2F), - 122.81(s, 2F), - 126.25(s, 2F), - 128.16(s, 2F).

[0057] Example 3 An oiling agent for anti - wicking polyester filaments, perfluorohexanesulfonyl acetic acid and its synthesis method

[0058] The structural formula of the oiling agent for anti - wicking polyester filaments is:

[0059] C 6 F 13 -SO 2 -CH 2 COOH (perfluorohexanesulfonyl acetic acid, R is a perfluoro - substituted alkyl group)

[0060] The preparation process is as follows:

[0061] In an enameled reactor, add 5 parts by weight of water, 1.5 parts by weight of sodium metabisulfite and 0.4 parts by weight of sodium hydroxide. After sufficient stirring, control the reaction temperature to about 60°C, add 0.75 parts by weight of perfluorohexylsulfonyl chloride dropwise, react for 2 hours, heat to 105°C and distill under reduced pressure to remove water. After the water is completely removed, cool to room temperature, add 10 parts by weight of ethanol into the reactor, stir to dissolve, press into a filter kettle to filter, remove the white solid sodium salt, and press the filtrate into another enameled reactor with an air compressor.

[0062] Dissolve 0.5 parts by weight of chloroacetic acid in 0.5 parts by weight of ethanol, add the chloroacetic acid-ethanol solution to the sodium perfluorohexanesulfinate-ethanol solution at room temperature, raise the temperature to 55°C, react for 2 hours, press into a filter kettle for filtration to remove white solid sodium chloride, and pump the filtrate into a closed organic solvent spray dryer to obtain solid perfluorohexanesulfonylacetic acid as a product with a yield of 94.67%.

[0063] Under the aforementioned HPLC-MS test conditions, the retention time of perfluorohexylsulfonylacetic acid is 7.67 min, and m / z is 440.78, which is the MH quasi-molecular ion peak of perfluorohexylsulfonylacetic acid. NMR of perfluorohexylsulfonylacetic acid: 19 F NMR (400MHz, CDCl 3 ): δ (ppm) -57.54 (s, 2F), -80.82 (s, 3F), -112.48 (s, 2F), -121.75 (s, 2F), -125.17 (s, 2F), -127.95 (s, 2F).

[0064] Example 4: Perfluorooctyl ethyl sulfonylacetic acid, an anti-wicking polyester yarn oiling agent, and a synthesis method

[0065] C 8 F 17 -CH(-CH 3 )-SO 2 -CH 2 COOH (perfluorooctylethylsulfonylacetic acid, R is a partially fluorinated alkyl group)

[0066] The synthesis method is:

[0067] In an enameled reactor, add 5 parts by weight of water, 1.5 parts by weight of sodium metabisulfite and 0.4 parts by weight of sodium hydroxide. After sufficient stirring, control the reaction temperature to about 60°C, add 1 part by weight of perfluorooctyl ethyl sulfonyl chloride dropwise, react for 2 hours, heat to 105°C and distill under reduced pressure to remove water. After the water is completely removed, cool to room temperature, add 10 parts by weight of ethanol into the reactor, stir to dissolve, press into a filter kettle to filter, remove the white solid sodium salt, and press the filtrate into another enameled reactor with an air compressor.

[0068] Dissolve 0.5 parts by weight of chloroacetic acid in 0.5 parts by weight of ethanol. Add the chloroacetic acid - ethanol solution to the sodium perfluorooctylethanesulfonate - ethanol solution at room temperature, then heat up to 55 °C. After reacting for 2 h, press it into a filtration kettle for filtration to remove the white solid sodium chloride. Pump the filtrate into a closed - type organic solvent spray dryer to obtain the solid product perfluorooctylethanesulfonylacetic acid, with a yield of 92.61%.

[0069] Under the test conditions of the above - mentioned liquid chromatography - mass spectrometry instrument, the retention time of perfluorooctylethanesulfonylacetic acid is 10.06 min, and m / z = 569.98, which is the M - H quasi - molecular ion peak of perfluorooctylethanesulfonylacetic acid. The NMR of perfluorooctylethanesulfonylacetic acid is as follows: 19 F NMR(400MHz,CDCl 3 ): δ(ppm) - 80.86(s, 3F), - 113.63(s, 4F), - 121.10(s, 2F), - 122.03(s, 2F), - 123.55(s, 2F), - 126.39(s, 2F), 128.64(s, 2F).

[0070] Example 5 Composition for sizing anti - wicking polyester filaments and its preparation

[0071] Prepare the fluorocarbon anti - wicking agent solution according to the formulation in Table 2, and then prepare the composition for sizing anti - wicking polyester filaments according to the formulation in Table 3. Among them, Q1 and Q2 are used as the comparative fluorocarbon anti - wicking agent solutions.

[0072] 1. Fluorocarbon anti - wicking agent solution and its preparation:

[0073] Table 2 Formulation of fluorocarbon anti - wicking agent solution (by parts by weight)

[0074]

[0075] Remarks: In Table 1, all raw materials are as follows:

[0076] A1 to A4 are perfluorohexylethanesulfonylacetic acid, perfluorooctanesulfonylacetic acid, perfluorohexanesulfonylacetic acid, and perfluorooctylethanesulfonylacetic acid in sequence.

[0077] Q1 is an existing emulsifier formulation, prepared by mixing glyceryl polyoxyethylene ether oleate: polyethylene glycol 400 oleate: sodium dodecylsulfonate in a mass ratio of 3:1:0.1 to form an emulsifier;

[0078] Q2 is potassium perfluorooctanesulfonate;

[0079] B is perfluorohexylethyl acrylate;

[0080] C is octadecyl methacrylate;

[0081] D is methyl methacrylate;

[0082] E is deionized water;

[0083] Preparation method: Mix the raw materials according to the formula in Table 1, stir at 300 rpm for 0.5 h to mix well, and use it as a fluorocarbon anti-wicking agent solution for later use.

[0084] 2. Preparation of oiling composition for anti-wicking polyester yarn

[0085] Table 3 Recipe of the oiling composition for anti-wicking polyester yarn (by weight)

[0086]

[0087] Note: In Table 3, the specific names of all raw materials are as follows:

[0088] Y is an existing silicone wax anti-wicking agent formula, which is a silicone wax emulsion prepared by C18 alkyl modified silicone oil: AEO3: AEO9: SDS: deionized water in a mass ratio of 8:3:1:0.1:140. Water needs to be dispersed in a high-speed stirring disperser at a speed of 1400 rpm and slowly added within 30 minutes to obtain silicone wax anti-wicking agent Y; wherein the C18 alkyl modified silicone oil is modified from n-octadecene to a hydrogen-containing silicone oil with a hydrogen content of 0.05% and a viscosity of 100 cP; AEO3 is a fatty alcohol polyoxyethylene ether with an EO addition number of 3, AEO9 is a fatty alcohol polyoxyethylene ether with an EO addition number of 9, and SDS is sodium dodecyl sulfonate.

[0089] Z is the SN-951 brand basic spinning oil of Sanyo Chemical Co., Ltd.

[0090] Preparation method: Take the raw materials according to the formula in Table 2 and mix them, stir them at 300 rpm for 0.5 h to mix them evenly, and use them as the oiling composition for anti-wicking polyester yarn for later use.

[0091] Example 6 Performance investigation of the composition for oiling anti-wicking polyester yarn

[0092] Performance tests were performed on six oiling compositions for anti-wicking polyester yarns, namely Experimental Example 1, Experimental Example 2, Experimental Example 3, Experimental Example 4, Comparative Example 1 and Comparative Example 2 prepared in Example 5, and the test indicators included wicking height and breaking strength.

[0093] Among them: The wicking height measurement method refers to T / CCFA01035-2018. The breaking strength measurement method refers to GB / T16604-2017. The fiber used for testing is polyester fiber. The spinning machine consists of a spinning channel, an oiling system, five sets of drawing and hot rollers, and one set of heat setting. The fiber preparation process is set with a draw ratio of 4.9, a relaxation ratio of 7.2%, 1000D / 192F, a spinning speed of 2600m / min, a setting temperature of 245°C. The oiling process is oiling by oil roller (emulsion oiling), and the total oil content of the yarn is 1.4%.

[0094] Table 4 Performance measurement results of wicking-resistant polyester filaments

[0095]

[0096] As can be seen from the results in Table 4, the wicking heights of the wicking-resistant polyester filaments in Experimental Examples 1 to 4 are significantly lower than those in Comparative Examples 1 and 2, and the strength shows no decrease compared with Comparative Examples 1 and 2. Since the same polyester filaments are used and the emulsifiers of the oiling compositions are different, the difference in effects is related to the emulsifier. And through the comparative analysis with Comparative Example 2 (the emulsifier is potassium perfluorooctane sulfonate), the effect of the present invention is related to the -SO 2 -CH 2 COOH group of the agent for oiling wicking-resistant polyester filaments.

[0097] The above has exemplarily illustrated the solution and effect of the present invention through specific embodiments. For those of ordinary skill in the art, under the inspiration of the general idea of the present invention, simple substitution / modification solutions that can be obtained without creative labor should fall within the protection scope of the present invention. For example, there are various similar groups of the R group in the agent for oiling wicking-resistant polyester filaments, which can be used by those of ordinary skill in the art, and based on the same principle, their effects can be expected; under the inspiration of the general synthesis route of the present invention, the synthesis process parameters of the agent for oiling wicking-resistant polyester filaments, including temperature and feeding ratio, can be adjusted conventionally, and the conventional adjustment of the temperature and feeding ratio should fall within the protection scope of the present invention.

Claims

1. An anti-wicking polyester yarn oiling agent, characterized in that: The structural formula of the anti-wicking polyester filament oiling agent is: R-SO2-CH2COOH, wherein R is a perfluorinated substituted alkyl group or a partially fluorinated substituted alkyl group.

2. The anti-wicking polyester yarn oiling agent according to claim 1, characterized in that: The perfluoro-substituted alkyl group is selected from any one of perfluorohexyl and perfluorooctyl; the partially fluorinated alkyl group is selected from any one of perfluorohexylethyl and perfluorooctylethyl.

3. The method for synthesizing the anti-wicking polyester yarn oiling agent according to claim 1, characterized in that: The steps include: S1: adding sodium pyrosulfite, sodium hydroxide, perfluoro-substituted alkyl sulfonyl chloride or partially fluorinated alkyl sulfonyl chloride into a water system to react and generate sodium perfluoro-substituted alkyl sulfinate or sodium partially fluorinated alkyl sulfinate; after the reaction is completed, removing water and adding ethanol to prepare an ethanol solution of sodium perfluoro-substituted alkyl sulfinate or sodium partially fluorinated alkyl sulfinate; S2: preparing a chloroacetic acid-ethanol solution, mixing it with the ethanol solution of the perfluoro-substituted sodium alkyl sulfinate or partially fluorinated sodium alkyl sulfinate obtained in step S1, and reacting to form the anti-wicking polyester filament oiling agent.

4. The method for synthesizing an anti-wicking polyester yarn oiling agent according to claim 3, characterized in that: The synthesis method further comprises the steps of: S3: After the reaction in step S2 is completed, the reaction system is filtered, and the filtrate is dried to remove the solvent to obtain the anti-wicking polyester filament oiling agent.

5. The method for synthesizing an anti-wicking polyester yarn oiling agent according to claim 3, characterized in that: The oiling agent for the anti-wicking polyester filament is perfluorohexyl sulfonylacetic acid, and the raw material of step S1 is perfluorohexyl sulfonyl chloride. In step S1, the weight ratio of water, sodium metabisulfite, sodium hydroxide, perfluorohexyl sulfonyl chloride and ethanol is 5:1.5:0.4:0.75:10, and the reaction temperature is about 60°C; when the chloroacetic acid-ethanol solution is prepared in step S2, the weight ratio of chloroacetic acid to ethanol is 1:1, and the reaction temperature is 55°C.

6. The method for synthesizing an anti-wicking polyester yarn oiling agent according to claim 3, characterized in that: The oiling agent for the anti-wicking polyester filament is perfluorohexyl ethyl sulfonylacetic acid, and the raw material of step S1 is perfluorohexyl ethyl sulfonyl chloride. In step S1, the weight ratio of water, sodium metabisulfite, sodium hydroxide, perfluorohexyl ethyl sulfonyl chloride and ethanol is 5:1.5:0.4:0.8:10, and the reaction temperature is about 60°C; when the chloroacetic acid-ethanol solution is prepared in step S2, the weight ratio of chloroacetic acid to ethanol is 1:1, and the reaction temperature is 55°C.

7. The method for synthesizing an anti-wicking polyester yarn oiling agent according to claim 3, characterized in that: The oiling agent for the anti-wicking polyester filament is perfluorooctane sulfonylacetic acid, and the raw material of step S1 is perfluorooctane sulfonyl chloride. In step S1, the weight ratio of water, sodium metabisulfite, sodium hydroxide, perfluorooctane sulfonyl chloride and ethanol is 5:1.5:0.4:1:10, and the reaction temperature is about 60°C; when the chloroacetic acid-ethanol solution is prepared in step S2, the weight ratio of chloroacetic acid to ethanol is 1:1, and the reaction temperature is 55°C.

8. The method for synthesizing an anti-wicking polyester yarn oiling agent according to claim 3, characterized in that: The oiling agent for the anti-wicking polyester filament is perfluorooctyl ethyl sulfonylacetic acid, and the raw material of step S1 is perfluorooctyl ethyl sulfonyl chloride. In step S1, the weight ratio of water, sodium metabisulfite, sodium hydroxide, perfluorooctyl ethyl sulfonyl chloride and ethanol is 5:1.5:0.4:1:10, and the reaction temperature is about 60°C; when the chloroacetic acid-ethanol solution is prepared in step S2, the weight ratio of chloroacetic acid to ethanol is 1:1, and the reaction temperature is 55°C.

9. An oiling composition for anti-wicking polyester yarn, made from a fluorocarbon anti-wicking agent solution, a silicone wax anti-wicking agent, and a spinning oil, characterized in that: The fluorocarbon anti-wicking agent solution contains a fluorocarbon monomer and an emulsifier. The structural formula of the emulsifier is: R-SO2-CH2COOH, wherein R is a perfluorinated substituted alkyl group or a partially fluorinated substituted alkyl group.

10. The oiling composition for anti-wicking polyester yarn according to claim 9, characterized in that: In the emulsifier, the perfluoro-substituted alkyl group is selected from any one of perfluorohexyl and perfluorooctyl; in the emulsifier, the partially fluorinated alkyl group is selected from any one of perfluorohexylethyl and perfluorooctylethyl.

11. The oiling composition for anti-wicking polyester yarn according to claim 9, characterized in that: The fluorocarbon anti-wicking agent solution is made of an emulsifier, a fluorocarbon monomer, a long-chain alkyl monomer, an auxiliary monomer, and deionized water; the fluorocarbon monomer is perfluorohexyl ethyl acrylate, the long-chain alkyl monomer is octadecyl methacrylate, and the auxiliary monomer is methyl methacrylate.

12. The oiling composition for anti-wicking polyester yarn according to claim 11, characterized in that: The weight ratio of the emulsifier, fluorocarbon monomer, long-chain alkyl monomer, auxiliary monomer and deionized water is 3:10:5:2:

80.

13. The oiling composition for anti-wicking polyester yarn according to claim 12, characterized in that: The weight ratio of the fluorocarbon anti-wicking agent solution, the silicone wax anti-wicking agent, and the spinning oil is 30:5:

65.

14. Use of the anti-wicking polyester yarn oiling agent according to claim 1 or 2 or the anti-wicking polyester yarn oiling composition according to any one of claims 9 to 13 in the oiling of polyester yarn anti-wicking agents.

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