Cotton-feeling finishing agent and preparation method thereof

Abstract

The invention belongs to the technical field of new materials, and particularly relates to a cotton-feeling finishing agent and a preparation method thereof. The cotton feeling finishing agent provided by the invention is prepared from 23 to 27 parts of quaternary amino-polyester-polysiloxane terpolymer, 2 to 3 parts of emulsifier, 5 to 7 parts of solvent and 75 to 80 parts of deionized water. The invention solves the technical problems that the traditional organic silicon softener can cause poor hydrophilicity and slippery hand feeling of the fabric, and the cotton or cotton blended fabric treated by the cotton feeling finishing agent provided by the invention can keep good hydrophilicity while being soft in hand feeling. The quaternary amino-polyester-polysiloxane terpolymer synthesized by the invention has a good fluffy and soft effect due to the quaternary ammonium salt and polyester structure in combination with a siloxane chain segment with a proper polymerization degree, and breaks through the limitation that the soft and oily hand feelings of a conventional softening agent are in direct proportion.

Description

Technical Field

[0001] The invention belongs to the technical field of new materials, and particularly relates to a cotton-feel finishing agent and a preparation method thereof. Background Art

[0002] During the process of processing and removing impurities (grease, wax, etc.) and high-temperature dyeing, cotton or cotton blended fabrics will become rough and stiff, and the comfort will deteriorate. Although traditional silicone softeners can improve the feel and wearability of fabrics, they are widely used in textile finishing. However, silicone softeners will cause the hydrophilicity of fabrics to deteriorate and the feel to be oily, changing the natural touch of cotton fabrics. As customers have higher and higher requirements for the quality of textiles, how to obtain an excellent soft and fluffy feel while maintaining the unique skin-friendly moisture absorption and breathability of cotton fabrics is a technical problem that needs to be solved urgently. Therefore, it is necessary to develop a finishing agent that can make the processed cotton or cotton blended fabrics fluffy and soft while maintaining good hydrophilicity. Summary of the invention

[0003] The technical problem to be solved by the present invention is to provide a cotton-feel finishing agent, which can make fabrics have an excellent soft and fluffy feel while maintaining the unique skin-friendly moisture absorption and air permeability of cotton fabrics.

[0004] To achieve the above object, the present invention provides a cotton feel finishing agent, which comprises the following components, by weight: 23 to 27 parts of a quaternary amino-polyester-polysiloxane terpolymer, 2 to 3 parts of an emulsifier, 5 to 7 parts of a solvent, and 75 to 80 parts of deionized water;

[0005] The quaternary amino-polyester-polysiloxane terpolymer is obtained by polymerizing hydrophilic polyester, double-terminal epoxy silicone oil and chain extender. The quaternary amino-polyester-polysiloxane terpolymer provided by the present invention can make the fabric have an excellent soft and fluffy feel while maintaining the skin-friendly moisture absorption and breathability of cotton fabric.

[0006] Preferably, the preparation method of the quaternary amino-polyester-polysiloxane terpolymer comprises the following steps:

[0007] S1, synthetic hydrophilic polyester;

[0008] S2. Synthesis of double-terminal epoxy silicone oil: Add terminal hydrogen silicone oil, allyl glycidyl ether, and chloroplatinic acid catalyst into the reaction kettle, raise the temperature to 40-60°C, and keep warm for 5.5-6.5h;

[0009] S3, adding the hydrophilic polyester described in step S1 and the double-terminal epoxy silicone oil described in step S2 into a reaction kettle at a molar ratio of (1-1.05):2, heating to 60-80° C., and keeping the temperature for 3.5-4.5 hours to obtain a polyester-polysiloxane copolymer;

[0010] S4, adding a chain extender, wherein the molar ratio of the chain extender to the double-terminal epoxy silicone oil is 1:(1-1.05), and after the chain extension is completed, removing the solvent to obtain a quaternary amino-polyester-polysiloxane terpolymer;

[0011] The chain extender is selected from tetramethylethylenediamine or tetramethylhexamethylenediamine;

[0012] The hydrophilic polyester is selected from one of hydrophilic polyester A and hydrophilic polyester B; the hydrophilic polyester A is obtained by polymerization of lactic acid and polyethylene glycol; the hydrophilic polyester B is obtained by polymerization of succinic acid, 1,4-butanediol and polyethylene glycol. The hydrophilic polyester provided by the present invention is a segment combination accidentally discovered in multiple experiments, which is block copolymerized with double-terminal epoxy silicone oil in a suitable proportion, so that the finished fabric is soft and non-greasy, showing a cotton-like feel.

[0013] Preferably, the molecular weight of the double-ended epoxy silicone oil in step S2 is 3000-8000;

[0014] Preferably, the molar ratio of the terminal hydrogen-containing silicone oil to allyl glycidyl ether in step S2 is 1:(2.0-2.05);

[0015] Preferably, the amount of the catalyst chloroplatinic acid in step S2 is 0.0001-0.0005% of the sum of the weights of the terminal hydrogenated silicone oil and allyl glycidyl ether; the temperature in step S4 is maintained at 80-85° C., and the insulation time of the temperature is 2.8-3.2 h;

[0016] Preferably, the adding method in step S4 is dropwise addition, and the dropwise addition time is 0.8 to 1.2 hours;

[0017] Preferably, in step S4, the solvent removal is that the quaternary amino-polyester-polysiloxane terpolymer is extracted and separated by an isoparaffin solvent whose mass is twice the weight of the reaction product, and then transferred to a reaction kettle to remove the isoparaffin solvent by vacuum distillation.

[0018] Preferably, the preparation method of the hydrophilic polyester A specifically comprises the following steps:

[0019] A1. Add 1.0-1.05 parts of lactic acid and 1.0-1.05 parts of ionic liquid catalyst to the reactor by mass fraction, stir, introduce nitrogen, replace oxygen for 14-16 minutes, heat to 175-180°C, and keep warm for 0.4-0.6 hours;

[0020] A2, adding 1.5-1.58 parts of polyethylene glycol by mass fraction, evacuating, heating at 175-180°C to 200-210°C, and keeping the temperature for 3.0-3.5 hours to obtain hydrophilic polyester A;

[0021] Preferably, the preparation method of the hydrophilic polyester B specifically comprises the following steps:

[0022] B1. Add 130-131 parts of succinic acid, 90-91 parts of 1,4-butanediol, and 120-121 parts of ionic liquid catalyst to the reactor by mass fraction, stir, introduce nitrogen, replace oxygen for 14-16 minutes, heat to 175-180°C, and keep warm for 0.4-0.6 hours;

[0023] B2, sampling and testing the polymerization degree to be qualified, adding polyethylene glycol PEG2000, the mass ratio of polyethylene glycol to succinic acid is (1.52-1.53):1, evacuating, heating from 175-180° C. to 200-210° C., keeping warm for 3.0-3.5 hours, to obtain hydrophilic polyester B;

[0024] Preferably, the polyethylene glycol is selected from one or a combination of PEG400, PEG600, PEG1000, and PEG2000.

[0025] Preferably, the ionic liquid catalyst is [BMIM]CL-BiCL3, which comprises the following components: 1-methylimidazole, 1-chlorobutane, toluene, and bismuth trichloride.

[0026] Preferably, the preparation method of the ionic liquid catalyst specifically comprises the following steps:

[0027] C1, add 82.0-82.1 parts of 1-methylimidazole, 96-97 parts of 1-chloro-n-butane, and 49-50 parts of toluene into a reaction kettle, and react at 60-100° C. to obtain chloro-1-butyl-3-methylimidazole;

[0028] C2, under nitrogen protection, 312-315 parts of bismuth trichloride were added dropwise for 1.8-2.2 hours, during which the jacket of the reactor was cooled by cooling water and the temperature was controlled at 30-40°C to obtain an ionic liquid catalyst [BMIM]CL-BiCL3;

[0029] The present invention synthesizes an acidic ionic liquid containing a butylmethylimidazole group. The ionic liquid is stable to water and air, has strong acidity, can replace inorganic acid and be applied to traditional acid-catalyzed reactions. It can be used as a catalyst, a reaction medium, and an extraction medium, and has broad application prospects. Traditional esterification reactions are mostly carried out using inorganic acids as catalysts. Compared with the technology of the present invention, the use of traditional inorganic acid catalysts requires the reaction temperature to be increased to 260°C, the reaction time to be extended to 8 hours, and a large amount of organic solvents need to be used. The waste acid remaining after the reaction will cause environmental pollution. The ionic liquid catalyst of the present invention is more environmentally friendly, has good stability, is non-volatile, has adjustable compatibility with organic matter, reduces the reaction temperature and time, fully improves the efficiency of the reaction, and saves energy.

[0030] Preferably, the emulsifier is selected from isomeric tridecanol polyoxyethylene ether 1307; the solvent is selected from ethylene glycol butyl ether. The ethylene glycol butyl ether used in the present invention as a solvent in the formula can not only dissolve the polymer, but also reduce the viscosity of the polymer, making emulsification easier, and also reduce the viscosity of the product, making it convenient to dilute and use.

[0031] Preferably, the cotton feel finishing agent comprises the following ingredients in parts by mass: 25 parts of quaternary amino-polyester-polysiloxane terpolymer, 2 parts of emulsifier, 6 parts of solvent, and 77 parts of deionized water.

[0032] Another aspect of the present invention provides a method for preparing a cotton feel finishing agent, which is characterized by comprising the following steps: adding an emulsifier, a solvent, and deionized water to a quaternary amino-polyester-polysiloxane terpolymer, mixing uniformly, and filtering to obtain the cotton feel finishing agent.

[0033] Compared with the prior art, the present invention has the following beneficial effects:

[0034] (1) The present invention provides a cotton-feel finishing agent that can make fabrics both soft and hydrophilic, which can improve the hydrophilicity of dyed fabrics and can be applied to pure cotton, polyester-cotton and polyester fabrics. The quaternary amino-polyester-polysiloxane terpolymer synthesized by the present invention has a good fluffy and soft effect due to its quaternary ammonium salt and polyester structure, combined with siloxane segments, breaking the limitation of conventional softeners that the softness is proportional to the oily feel, and is of great significance to improving the added value of textiles and increasing international competitiveness.

[0035] (2) The molecular weight of the double-terminal epoxy silicone oil of the present invention is preferably 3000-8000. The quaternary amino-polyester-polysiloxane terpolymer synthesized by reacting the double-terminal epoxy silicone oil within this molecular weight range with a hydrophilic polyester and a chain extender can make the fabric have a better cotton feel.

[0036] (3) The bismuth-containing ionic liquid high-efficiency catalyst used in the present invention as a catalyst for the synthesis of hydrophilic polyesters has innovatively improved the catalytic efficiency of the esterification polycondensation reaction, greatly reduced the temperature of the polycondensation reaction from 270-290°C required for the traditional polyester synthesis temperature to 200-210°C, and greatly shortened the reaction time from the traditional 8 hours to 4 hours. There is no similar report, which is innovative. In addition, because the melting point of polyester (>120°C) is much higher than the reaction temperature of polyester-polysiloxane (60-85°C), the epoxy group of the terminal epoxy silicone oil will decompose under high temperature conditions. The present invention utilizes the good solubility of the ionic liquid to dissolve the polyester in the ionic liquid, and the condensation reaction between the polyester and the terminal epoxy silicone oil can proceed smoothly, effectively reducing the reaction temperature and increasing the reaction rate. DETAILED DESCRIPTION

[0037] The present invention is further described below in conjunction with the examples. It should be noted that the following examples are only used to explain the present invention, but not to limit the present invention. The experimental methods used in the following examples are conventional methods unless otherwise specified. The materials, reagents, etc. used in the following examples, if not otherwise specified, can be obtained through commercial channels. Unless otherwise specified, the percentages mentioned in the present invention are all mass percentages.

[0038] Isoparaffin solvent was purchased from ExxonMobil Chemical (product name: ISOPAR E);

[0039] The end-hydrogenated silicone oil was purchased from Jiangxi Bluestar Starspark Organic Silicone Co., Ltd., product name: Hydrogenated silicone oil STARSIL620V;

[0040] Allyl glycidyl ether was purchased from Osaka Soda Co Ltd, Japan. Product name: NEOALLYL TM G;

[0041] Polyethylene glycol was purchased from Nanjing Gutian Chemical Co., Ltd., product names: PEG400, PEG600, PEG1000, PEG2000.

[0042] Example 1

[0043] A cotton-feel finishing agent, the specific preparation method comprises the following steps:

[0044] 1. Prepare an ionic liquid catalyst, specifically comprising the following steps:

[0045] C1. Add 82.0 parts of 1-methylimidazole, 96.5 parts of 1-chlorobutane and 50 parts of toluene into a reaction kettle, and react to obtain chloro-1-butyl-3-methylimidazole.

[0046] C2. Cooling water was passed through the jacket of the reactor to cool it down and the temperature was controlled at 40°C. Under nitrogen protection, 315 parts of bismuth trichloride were added dropwise for 2 hours to obtain the ionic liquid catalyst [BMIM]CL-BiCL3.

[0047] 2. Synthesize quaternary amino-polyester-polysiloxane terpolymer, the specific steps are as follows:

[0048] S1. Synthesize hydrophilic polyester A. The specific steps are as follows:

[0049] A1. Add 1.02 parts of lactic acid and 1.0 parts of ionic liquid catalyst to the reactor by mass fraction, stir, introduce nitrogen, replace oxygen for 15 minutes, gradually heat up at a heating rate of 2.5℃ / min to 110℃, water vapor begins to be discharged, continue to control the heating rate of 2.5℃ / min to 180℃, and keep warm for 0.5 hours;

[0050] A2, add 1.55 parts of polyethylene glycol PEG400 by mass fraction, evacuate to 266 Pa, heat to 210 ° C, and keep warm for 3.5 hours to obtain hydrophilic polyester A.

[0051] S2, synthetic double-ended epoxy silicone oil:

[0052] Add 1 part of terminal hydrogenated silicone oil, 2.03 parts of allyl glycidyl ether, and 0.0003% of chloroplatinic acid catalyst based on the sum of the weight of terminal hydrogenated silicone oil and allyl glycidyl ether into the reactor, heat to 50°C, and keep warm for 6 hours to obtain a double-terminal epoxy silicone oil with a molecular weight of 6000.

[0053] S3. Add the hydrophilic polyester described in step S1 and the double-terminal epoxy silicone oil described in step S2 into the reaction kettle at a molar ratio of 1:2, raise the temperature to 70° C., and keep the temperature for 4 hours to obtain a polyester-polysiloxane copolymer.

[0054] S4. The temperature is maintained at 83°C, and tetramethylethylenediamine (1 times the weight of double-ended epoxy silicone oil) is added dropwise for 1 hour. Chain extension is performed, and the heat is maintained for 3 hours. The solvent is removed, and the reaction product is extracted and separated by passing through an isoparaffin solvent (2 times the weight of the reaction product) in an extraction tower. The quaternary amino-polyester-polysiloxane terpolymer is extracted by the isoparaffin solvent, flows out from the upper part of the extraction tower, and is transferred to a reactor to remove the isoparaffin solvent by vacuum distillation to obtain a quaternary amino-polyester-polysiloxane terpolymer.

[0055] 3. In parts by mass, add 2 parts of emulsifier, 5 parts of ethylene glycol butyl ether and 75 parts of deionized water to 25 parts of quaternary amino-polyester-polysiloxane terpolymer, mix well and filter to obtain.

[0056] Example 2

[0057] A cotton-feel finishing agent, the specific preparation method comprises the following steps:

[0058] 1. Prepare an ionic liquid catalyst, specifically comprising the following steps:

[0059] C1. Add 82.1 parts of 1-methylimidazole, 96.0 parts of 1-chlorobutane and 49 parts of toluene into a reaction kettle, and react to obtain chloro-1-butyl-3-methylimidazole.

[0060] C2. Cooling water was passed through the jacket of the reactor to cool it down and the temperature was controlled at 35°C. Under nitrogen protection, 313 parts of bismuth trichloride were added dropwise for 1.8 hours to obtain the ionic liquid catalyst [BMIM]CL-BiCL3.

[0061] 2. Synthesize quaternary amino-polyester-polysiloxane terpolymer, the specific steps are as follows:

[0062] S1. Synthetic hydrophilic polyester A:

[0063] A1. Add 1.0 part of lactic acid and 1.0 part of ionic liquid catalyst to the reactor by mass fraction, stir, introduce nitrogen, replace oxygen for 14 minutes, heat up to 110°C at a rate of 2°C / min, water vapor begins to be discharged, continue to control the heating rate to 175°C at 2°C / min, and keep warm for 0.4 hours;

[0064] A2. Add 1.5 parts of polyethylene glycol PEG400 by mass fraction, evacuate to 268 Pa, heat to 200°C and keep warm for 3.2 hours to obtain hydrophilic polyester A.

[0065] S2, synthetic double-ended epoxy silicone oil:

[0066] Add 1 part of terminal hydrogenated silicone oil, 2 parts of allyl glycidyl ether, and 0.0005% of chloroplatinic acid catalyst based on the sum of the weight of terminal hydrogenated silicone oil and allyl glycidyl ether into the reactor, heat to 40°C, and keep warm for 5.5 hours to obtain double-terminal epoxy silicone oil with a molecular weight of 8000.

[0067] S3. Add the hydrophilic polyester described in step S1 and the double-terminal epoxy silicone oil described in step S2 into the reaction kettle at a molar ratio of 1.03:2, raise the temperature to 80° C., and keep the temperature for 3.5 hours to obtain a polyester-polysiloxane copolymer.

[0068] S4, the temperature is maintained at 85 ° C, the amount of the substance is 0.952 times the weight of the double-ended epoxy silicone oil, tetramethylhexanediamine is added for 0.8 hours, the chain is extended, the temperature is kept for 2.8 hours, the solvent is removed, and the reaction product is extracted and separated by an isoparaffin solvent twice the weight of the reaction product in the extraction tower. The quaternary amino-polyester-polysiloxane terpolymer is extracted by the isoparaffin solvent, flows out from the upper part of the extraction tower, and is transferred to the reactor for vacuum distillation to remove the isoparaffin solvent to obtain a quaternary amino-polyester-polysiloxane terpolymer.

[0069] 3. Add 3 parts of emulsifier, 7 parts of ethylene glycol butyl ether and 80 parts of deionized water to 23 parts of quaternary amino-polyester-polysiloxane terpolymer, mix well and filter to obtain.

[0070] Example 3

[0071] A cotton-feel finishing agent, the specific preparation method comprises the following steps:

[0072] 1. Prepare an ionic liquid catalyst, specifically comprising the following steps:

[0073] C1. Add 82.1 parts of 1-methylimidazole, 97 parts of 1-chlorobutane and 49.5 parts of toluene into a reaction kettle, and react to obtain chloro-1-butyl-3-methylimidazole.

[0074] C2. Cooling water was passed through the jacket of the reactor to cool it down and the temperature was controlled at 30°C. Under nitrogen protection, 312 parts of bismuth trichloride were added dropwise for 2.2 hours to obtain the ionic liquid catalyst [BMIM]CL-BiCL3.

[0075] 2. Synthesize quaternary amino-polyester-polysiloxane terpolymer, the specific steps are as follows:

[0076] S1. Synthetic hydrophilic polyester A:

[0077] A1. Add 1.0 part of lactic acid and 1.0 part of ionic liquid catalyst to the reactor by mass fraction, stir, introduce nitrogen, replace oxygen for 16 minutes, heat to 110°C at a heating rate of 3°C / min, water vapor begins to be discharged, continue to control the heating rate to 178°C at 3°C / min, and keep warm for 0.6 hours;

[0078] A2, add 1.58 parts of polyethylene glycol PEG400 by mass fraction, evacuate to 267 Pa, heat to 205 ° C, and keep warm for 3 hours to obtain hydrophilic polyester A.

[0079] S2, synthetic double-ended epoxy silicone oil:

[0080] Add 1 part of terminal hydrogenated silicone oil, 2.05 parts of allyl glycidyl ether, and 0.0001% of chloroplatinic acid catalyst based on the sum of the weight of terminal hydrogenated silicone oil and allyl glycidyl ether into the reactor, heat to 60°C, and keep warm for 5.5 hours to obtain double-terminal epoxy silicone oil with a molecular weight of 3000.

[0081] S3. Add the hydrophilic polyester described in step S1 and the double-terminal epoxy silicone oil described in step S2 into the reaction kettle at a molar ratio of 1.05:2, raise the temperature to 60° C., and keep the temperature for 4.5 hours to obtain a polyester-polysiloxane copolymer.

[0082] S4, the temperature is maintained at 60°C, the amount of tetramethylethylenediamine (0.98 times the weight of double-ended epoxy silicone oil) is added dropwise for 1.2 hours, the chain is extended, the heat is maintained for 3.2 hours, the solvent is removed, and the reaction product is extracted and separated in an extraction tower through an isoparaffin solvent that is twice the weight of the reaction product. The quaternary amino-polyester-polysiloxane terpolymer is extracted by the isoparaffin solvent, flows out from the upper part of the extraction tower, and is transferred to a reactor to remove the isoparaffin solvent by vacuum distillation to obtain a quaternary amino-polyester-polysiloxane terpolymer.

[0083] 3. Add 2.5 parts of emulsifier, 7 parts of ethylene glycol butyl ether and 78 parts of deionized water to 27 parts of quaternary amino-polyester-polysiloxane terpolymer, mix well and filter to obtain.

[0084] Example 4

[0085] A cotton-feel finishing agent, the specific preparation method comprises the following steps:

[0086] 1. Prepare an ionic liquid catalyst, specifically comprising the following steps:

[0087] C1. Add 82.0 parts of 1-methylimidazole, 96.5 parts of 1-chlorobutane and 50 parts of toluene into a reaction kettle, and react to obtain chloro-1-butyl-3-methylimidazole.

[0088] C2. Cooling water was passed through the jacket of the reactor to cool it down and the temperature was controlled at 40°C. Under nitrogen protection, 315 parts of bismuth trichloride were added dropwise for 2 hours to obtain the ionic liquid catalyst [BMIM]CL-BiCL3.

[0089] 2. Synthesize quaternary amino-polyester-polysiloxane terpolymer, the specific steps are as follows:

[0090] S1. Synthetic hydrophilic polyester B:

[0091] B1. Add 130 parts of succinic acid, 91 parts of 1,4-butanediol and 120 parts of ionic liquid catalyst to the reactor by mass fraction, stir, introduce nitrogen, replace oxygen for 15 minutes, heat up at a rate of 2.5℃ / min to 110℃, water vapor begins to be discharged, continue to control the heating rate at 2.5℃ / min to 180℃, and keep warm for 0.5 hours;

[0092] B2. If the degree of polymerization is qualified after sampling and testing, polyethylene glycol PEG2000 is added, and the mass ratio of polyethylene glycol to succinic acid is 1.52:1. Vacuum the mixture, heat to 210°C, and keep warm for 3.5 hours to obtain hydrophilic polyester B.

[0093] S2, synthetic double-ended epoxy silicone oil:

[0094] Add 1 part of terminal hydrogen silicone oil, 2 parts of allyl glycidyl ether, and 0.0001% of chloroplatinic acid catalyst based on the sum of the weight of terminal hydrogen silicone oil and allyl glycidyl ether into the reactor, heat to 50°C, and keep warm for 6 hours to obtain a double-terminal epoxy silicone oil with a molecular weight of 3000.

[0095] S3. Add the hydrophilic polyester described in step S1 and the double-terminal epoxy silicone oil described in step S2 into the reaction kettle at a molar ratio of 1:2, raise the temperature to 70° C., and keep the temperature for 4 hours to obtain a polyester-polysiloxane copolymer.

[0096] S4. The temperature is maintained at 80°C, tetramethylhexanediamine is added dropwise for 1 hour, chain extension is performed, the temperature is maintained for 3 hours, and the solvent is removed. The reaction product passes through an isoparaffin solvent that is 2 times the weight of the reactants in an extraction tower, and is extracted and separated. The quaternary amino-polyester-polysiloxane terpolymer is extracted by the isoparaffin solvent, flows out from the upper part of the extraction tower, and is transferred to a reactor to remove the isoparaffin solvent by vacuum distillation to obtain a quaternary amino-polyester-polysiloxane terpolymer.

[0097] 3. In parts by mass, add 2 parts of emulsifier, 5 parts of ethylene glycol butyl ether and 75 parts of deionized water to 25 parts of quaternary amino-polyester-polysiloxane terpolymer, mix well and filter to obtain.

[0098] Example 5

[0099] A cotton-feel finishing agent, the specific preparation method comprises the following steps:

[0100] 1. Prepare an ionic liquid catalyst, specifically comprising the following steps:

[0101] C1. Add 82.1 parts of 1-methylimidazole, 96 parts of 1-chlorobutane and 49 parts of toluene into a reaction kettle, and react to obtain chloro-1-butyl-3-methylimidazole.

[0102] C2. Cooling water was passed through the jacket of the reactor to cool it down and the temperature was controlled at 30°C. Under nitrogen protection, 312 parts of bismuth trichloride were added dropwise for 1.8 hours to obtain the ionic liquid catalyst [BMIM]CL-BiCL3.

[0103] 2. Synthesize quaternary amino-polyester-polysiloxane terpolymer, the specific steps are as follows:

[0104] S1. Synthetic hydrophilic polyester B:

[0105] B1. Add 131 parts of succinic acid, 90 parts of 1,4-butanediol and 121 parts of ionic liquid catalyst to the reactor by mass fraction, stir, introduce nitrogen, replace oxygen for 16 minutes, heat up at a rate of 2°C / min to 110°C, water vapor begins to be discharged, continue to control the heating rate at 2°C / min to 175°C, and keep warm for 0.6 hours;

[0106] B2. If the degree of polymerization is qualified after sampling and testing, polyethylene glycol PEG2000 is added, and the mass ratio of polyethylene glycol to succinic acid is 1.53:1. Vacuum the mixture, heat to 200°C, and keep warm for 3.0 hours to obtain hydrophilic polyester B.

[0107] S2, synthetic double-ended epoxy silicone oil:

[0108] Add 1 part of terminal hydrogenated silicone oil, 2.05 parts of allyl glycidyl ether, and 0.0003% of chloroplatinic acid catalyst based on the sum of the weight of terminal hydrogenated silicone oil and allyl glycidyl ether into the reactor, heat to 60°C, and keep warm for 5.5 hours to obtain a double-terminal epoxy silicone oil with a molecular weight of 6000.

[0109] S3. Add the hydrophilic polyester described in step S1 and the double-terminal epoxy silicone oil described in step S2 into the reaction kettle at a molar ratio of 1.03:2, raise the temperature to 80° C., and keep the temperature for 3.5 hours to obtain a polyester-polysiloxane copolymer.

[0110] S4. The temperature is maintained at 83°C, tetramethylethylenediamine is added dropwise for 1 hour, chain extension is performed, the temperature is maintained for 2.8 hours, and the solvent is removed. The reaction product passes through an isoparaffin solvent that is 2 times the weight of the reactants in an extraction tower, and is extracted and separated. The quaternary amino-polyester-polysiloxane terpolymer is extracted by the isoparaffin solvent, flows out from the upper part of the extraction tower, and is transferred to a reactor to remove the isoparaffin solvent by vacuum distillation to obtain a quaternary amino-polyester-polysiloxane terpolymer.

[0111] 3. Add 3 parts of emulsifier, 7 parts of ethylene glycol butyl ether and 80 parts of deionized water to 23 parts of quaternary amino-polyester-polysiloxane terpolymer, mix well and filter to obtain.

[0112] Example 6

[0113] A cotton-feel finishing agent, the specific preparation method comprises the following steps:

[0114] 1. Prepare an ionic liquid catalyst, specifically comprising the following steps:

[0115] C1. Add 82.0 parts of 1-methylimidazole, 97 parts of 1-chlorobutane and 49.5 parts of toluene into a reaction kettle, and react to obtain chloro-1-butyl-3-methylimidazole.

[0116] C2. Cooling water was passed through the jacket of the reactor to cool it down and the temperature was controlled at 35°C. Under nitrogen protection, 313 parts of bismuth trichloride were added dropwise for 2.2 hours to obtain the ionic liquid catalyst [BMIM]CL-BiCL3.

[0117] 2. Synthesize quaternary amino-polyester-polysiloxane terpolymer, the specific steps are as follows:

[0118] S1. Synthetic hydrophilic polyester B:

[0119] B1. Add 130.5 parts of succinic acid, 90.5 parts of 1,4-butanediol and 120.5 parts of ionic liquid catalyst to the reactor by mass fraction, stir, introduce nitrogen, replace oxygen for 14 minutes, heat up at a rate of 3°C / min to 110°C, water vapor begins to be discharged, continue to control the heating rate to 3°C / min to 178°C, and keep warm for 0.4 hours;

[0120] B2. If the degree of polymerization is qualified after sampling and testing, polyethylene glycol PEG2000 is added, and the mass ratio of polyethylene glycol to succinic acid is 1.52:1. Vacuum the mixture, heat to 210°C, and keep warm for 3.3 hours to obtain hydrophilic polyester B.

[0121] S2, synthetic double-ended epoxy silicone oil:

[0122] Add 1 part of terminal hydrogenated silicone oil, 2.03 parts of allyl glycidyl ether, and 0.0005% of chloroplatinic acid catalyst based on the sum of the weight of terminal hydrogenated silicone oil and allyl glycidyl ether into the reactor, heat to 40°C, and keep warm for 6.5 hours to obtain double-terminal epoxy silicone oil with a molecular weight of 8000.

[0123] S3. Add the hydrophilic polyester described in step S1 and the double-terminal epoxy silicone oil described in step S2 into the reaction kettle at a molar ratio of 1.05:2, raise the temperature to 60° C., and keep the temperature for 4.5 hours to obtain a polyester-polysiloxane copolymer.

[0124] S4. The temperature is maintained at 85°C, tetramethylhexanediamine is added dropwise for 1.2 hours, the chain is extended, the temperature is maintained for 3.2 hours, the solvent is removed, and the reaction product is extracted and separated by passing through an isoparaffin solvent that is 2 times the weight of the reactants in an extraction tower. The quaternary amino-polyester-polysiloxane terpolymer is extracted by the isoparaffin solvent, flows out from the upper part of the extraction tower, and is transferred to a reactor to remove the isoparaffin solvent by vacuum distillation to obtain a quaternary amino-polyester-polysiloxane terpolymer.

[0125] 3. Add 2.5 parts of emulsifier, 7 parts of ethylene glycol butyl ether and 78 parts of deionized water to 27 parts of quaternary amino-polyester-polysiloxane terpolymer, mix well and filter to obtain.

[0126] Comparative Example 1

[0127] A cotton-feel finishing agent is basically the same as Example 1, except that the ratio of the amount of hydrophilic polyester to the double-terminal epoxy silicone oil in step S3 is 1.02:1; and no quaternary ammonium group is added in step S4, and the polyester-polyether-polysiloxane terpolymer is obtained by the reaction. The specific preparation steps are as follows:

[0128] 1. Prepare an ionic liquid catalyst, specifically comprising the following steps:

[0129] C1. Add 82.0 parts of 1-methylimidazole, 96.5 parts of 1-chlorobutane and 50 parts of toluene into a reaction kettle, and react to obtain chloro-1-butyl-3-methylimidazole.

[0130] C2. Cooling water was passed through the jacket of the reactor to cool it down and the temperature was controlled at 40°C. Under nitrogen protection, 315 parts of bismuth trichloride were added dropwise to obtain the ionic liquid catalyst [BMIM]CL-BiCL3.

[0131] 2. Synthesize polyether-polyester-polysiloxane terpolymer, the specific steps are as follows:

[0132] S1. Synthesize hydrophilic polyester A. The specific steps are as follows:

[0133] A1. Add 1.02 parts of lactic acid and 1.0 parts of ionic liquid catalyst to the reactor by mass fraction, stir, introduce nitrogen, replace oxygen for 15 minutes, gradually heat up at a heating rate of 2.5℃ / min to 110℃, water vapor begins to be discharged, continue to control the heating rate of 2.5℃ / min to 180℃, and keep warm for 0.5 hours;

[0134] A2, add 1.55 parts of polyethylene glycol PEG400 by mass fraction, evacuate to 266 Pa, heat to 210 ° C, and keep warm for 3.5 hours to obtain hydrophilic polyester A.

[0135] S2, synthetic double-ended epoxy silicone oil:

[0136] Add 1 part of terminal hydrogenated silicone oil, 2.03 parts of allyl glycidyl ether, and 0.0003% of chloroplatinic acid catalyst based on the sum of the weight of terminal hydrogenated silicone oil and allyl glycidyl ether into the reactor, heat to 50°C, and keep warm for 6 hours to obtain a double-terminal epoxy silicone oil with a molecular weight of 6000.

[0137] S3. Add the hydrophilic polyester described in step S1 and the double-terminal epoxy silicone oil described in step S2 into the reaction kettle at a molar ratio of 1.02:1, raise the temperature to 70° C., and keep the temperature for 4 hours to obtain a polyester-polysiloxane copolymer.

[0138] S4, removing the solvent, the reaction product is extracted and separated by passing through an isoparaffin solvent twice the weight of the reaction product in an extraction tower, the quaternary amino-polyester-polysiloxane terpolymer is extracted by the isoparaffin solvent, flows out from the upper part of the extraction tower, and is transferred to a reactor to remove the isoparaffin solvent by vacuum distillation to obtain a polyether-polyester-polysiloxane terpolymer.

[0139] 3. In parts by mass, add 2 parts of emulsifier, 5 parts of ethylene glycol butyl ether and 75 parts of deionized water to 25 parts of polyether-polyester-polysiloxane terpolymer, mix well and filter to obtain.

[0140] Comparative Example 2

[0141] A cotton-feel finishing agent is basically the same as Example 1, the only difference being that: hydrophilic polyester is not synthesized, and the chain is directly extended after the synthesis of the double-terminal epoxy silicone oil, that is, the polyester polyether chain segment is not connected, and the reaction obtains a quaternary ammonium-polysiloxane binary copolymer, and the specific steps are as follows:

[0142] 1. Synthesize quaternary amino-polysiloxane copolymer, the specific steps are as follows:

[0143] S1, synthetic double-ended epoxy silicone oil:

[0144] Add 1 part of terminal hydrogenated silicone oil, 2.03 parts of allyl glycidyl ether, and 0.0003% of chloroplatinic acid catalyst based on the sum of the weight of terminal hydrogenated silicone oil and allyl glycidyl ether into the reactor, heat to 50°C, and keep warm for 6 hours to obtain a double-terminal epoxy silicone oil with a molecular weight of 6000.

[0145] S2. The temperature is maintained at 83°C, and tetramethylethylenediamine is added dropwise for 1 hour. The mass of tetramethylethylenediamine is 1.05 times the mass of the double-ended epoxy silicone oil. The chain is extended, and the heat is maintained for 3 hours. The solvent is removed. The reaction product passes through an isoparaffin solvent that is 2 times the weight of the reaction product in an extraction tower, and is extracted and separated. The quaternary amino-polysiloxane binary copolymer is extracted by the isoparaffin solvent, flows out from the upper part of the extraction tower, and is transferred to a reactor to remove the isoparaffin solvent by vacuum distillation to obtain a quaternary amino-polysiloxane binary copolymer.

[0146] 2. In parts by mass, add 2 parts of emulsifier, 5 parts of ethylene glycol butyl ether and 75 parts of deionized water to 25 parts of quaternary amino-polysiloxane binary copolymer, mix well and filter to obtain.

[0147] Comparative Example 3

[0148] A cotton-feel finishing agent is basically the same as Example 1, the only difference being that: hydrophilic polyester is not synthesized, and a double-terminal epoxy polyether is introduced after synthesizing a double-terminal epoxy silicone oil, and tetramethylethylenediamine is added dropwise for chain extension, that is, only a polyether segment is introduced instead of a polyether polyester segment, and a polyether-amino-polysiloxane terpolymer is obtained by the reaction, and the specific steps are as follows:

[0149] 1. Synthesize polyether-amino-polysiloxane terpolymer, the specific steps are as follows:

[0150] S1, synthetic double-ended epoxy silicone oil:

[0151] Add 1 part of terminal hydrogenated silicone oil, 2.03 parts of allyl glycidyl ether, and 0.0003% of chloroplatinic acid catalyst based on the sum of the weight of terminal hydrogenated silicone oil and allyl glycidyl ether into the reactor, heat to 50°C, and keep warm for 6 hours to obtain a double-terminal epoxy silicone oil with a molecular weight of 6000.

[0152] S2. Keep the temperature at 60°C, add tetramethylethylenediamine dropwise for 1 hour. The amount of tetramethylethylenediamine is twice that of the double-terminal epoxy silicone oil. Extend the chain and keep warm for 3 hours to obtain the double-terminal amino silicone oil.

[0153] S3. Raise the temperature to 80°C, and add double-ended epoxy polyether dropwise at a substance amount ratio of 1:1.01, wherein the substance amount of the double-ended epoxy polyether is 1.01 times that of the double-ended amino silicone oil. Add dropwise for 1 hour, and then keep warm for 3 hours to obtain a polyether-amino-polysiloxane terpolymer. Remove the solvent, and the reaction product is extracted and separated in an extraction tower by passing through an isoparaffin solvent that is 2 times the weight of the reaction product. The polyether-amino-polysiloxane terpolymer is extracted by the isoparaffin solvent, flows out from the upper part of the extraction tower, and is transferred to a reactor to remove the isoparaffin solvent by vacuum distillation to obtain a polyether-amino-polysiloxane terpolymer.

[0154] 2. In parts by mass, add 2 parts of emulsifier, 5 parts of ethylene glycol butyl ether and 75 parts of deionized water to 25 parts of polyether-amino-polysiloxane terpolymer, mix well and filter to obtain.

[0155] Test Example 1: Sample solid content test

[0156] Test method: Use an analytical balance to accurately weigh about 2 grams of the original sample in a watch glass, place it in an oven, dry it at 105℃-108℃ for 3 hours, take it out and weigh it, put it in the oven again, treat it under the same conditions for 30 minutes, take it out and weigh it again, repeat this twice. Compare the three data to see if constant weight is reached, and then calculate the solid content according to the formula: solid content = dry constant weight / original weight of material × 100%, the results are shown in the following table.

[0157] Sample solid content test results table

[0158] Comparative samples Appearance Solid content Comparative samples Appearance Solid content Example 1 Yellow liquid 81.7％ Example 6 Yellow liquid 84.1％ Example 2 Yellow liquid 84.5％ Comparative Example 1 Yellow liquid 82％ Example 3 Yellow liquid 82.4％ Comparative Example 2 Yellow liquid 85％ Example 4 Yellow liquid 83.5％ Comparative Example 3 Yellow liquid 84％ Example 5 Yellow liquid 83.0％ / / /

[0159] It can be seen from the above table that the solid content of the cotton feel finishing agent of the present invention meets the national standards.

[0160] Test Example 2: Hydrophilicity Test

[0161] Test fabric: pure cotton knitted double-sided white fabric.

[0162] Test method: Hydrophilicity (Capillary effect test standard: FZ / T 01071 Textile capillary effect test method). The test results are shown in the following table.

[0163] Hydrophilicity test results table

[0164] Comparative samples Capillary effect Comparative samples Capillary effect blank 13.1cm Example 5 14.9cm Example 1 15cm Example 6 14.8cm Example 2 14.8cm Comparative Example 1 15cm Example 3 14.7cm Comparative Example 2 0.3cm Example 4 15cm Comparative Example 3 13.4cm

[0165] From the above results, it can be seen that the capillary effect of Comparative Example 2 is only 0.3 cm, which is much weaker than 14.8-15 cm of Examples 1-6, while the capillary effect of Comparative Example 1 is equivalent to that of Examples 1-6, and the capillary effect of Comparative Example 3 is slightly weaker than that of Examples 1-6. This is because the quaternary amino-polysiloxane binary copolymer used in Comparative Example 2 does not have a hydrophilic polyester polyether segment, so it has no hydrophilicity. The polyether-amino-polysiloxane terpolymer used in Comparative Example 3 is not connected with a polyester segment, and its hydrophilicity is weaker than that of Examples 1-6 using the hydrophilic polyester of the present invention. It can be seen that the hydrophilic polyester provided by the present invention, that is, the hydrophilic polyester polyether segment, can make the cotton cloth treated with the finishing agent have better hydrophilicity.

[0166] Test Example 3: Hand Feel Evaluation

[0167] Test fabric: pure cotton knitted double-sided white fabric.

[0168] Test method: A test team of 5 experienced personnel will rate the softness, dryness (the drier the less greasy), and fluffiness of the samples by touching or wrinkling them with their hands, from hard (0) to very soft (10). The final result will be a weighted average of the scores of the 5 testers.

[0169] Hand feel evaluation results table

[0170] Comparative samples Softness Dryness Fluffiness blank 0 0 0 Example 1 10 10 8 Example 2 9 10 8 Example 3 9 9 9 Example 4 10 9 8 Example 5 10 10 7 Example 6 9 10 8 Comparative Example 1 4 9 0 Comparative Example 2 9 0 10 Comparative Example 3 8 9 7

[0171] From the results in the above table, it can be seen that the softness of Examples 1 to 6 is 9 to 10 points, the dryness is 9 to 10 points, and the fluffiness is 7 to 9 points, and the hand feel is good. The dryness of Comparative Example 1 is equivalent to that of the Examples, with a softness of 4 points and a fluffiness of 0 points. This is because the polyether-polyester-polysiloxane terpolymer used in Comparative Example 1 does not introduce a quaternary ammonium group, resulting in a poor hand feel; Comparative Example 2 has a softness of 9 points and a fluffiness of 10 points, which is equivalent to the Examples, but its dryness is 0 points, which is because it does not introduce the hydrophilic polyester of the present invention; Comparative Example 3 has a dryness of 9 points and a fluffiness of 7 points, which is equivalent to the Examples, but its softness is 8 points. This is because the polyether-amino-polysiloxane terpolymer used in Comparative Example 3 does not have a polyester segment, so the hand feel is slippery and there is no cotton feeling.

[0172] In summary, the quaternary amino-polyester-polysiloxane terpolymer provided by the present invention introduces a specific hydrophilic polyester segment, which can make the cotton feel finishing agent give the cotton cloth good hydrophilicity, and at the same time, the introduction of quaternary ammonium groups makes the cotton cloth have a soft, dry and fluffy cotton feel. In addition, the ionic liquid catalyst prepared by the present invention effectively realizes the synthesis of double-terminal epoxy silicone oil, thereby facilitating the production of the quaternary amino-polyester-polysiloxane terpolymer of the present invention.

Claims

1. A cotton feeling finishing agent, characterized in that: The composition comprises the following components by weight: 23 to 27 parts of quaternary amino-polyester-polysiloxane terpolymer, 2 to 3 parts of emulsifier, 5 to 7 parts of solvent, and 75 to 80 parts of deionized water; The quaternary amino-polyester-polysiloxane terpolymer is obtained by polymerizing a hydrophilic polyester, a double-terminal epoxy silicone oil and a chain extender.

2. The cotton feeling finishing agent according to claim 1, characterized in that The molecular weight of the double-ended epoxy silicone oil is 3000-8000.

3. The cotton feeling finishing agent according to claim 1, characterized in that The preparation method of the quaternary amino-polyester-polysiloxane terpolymer comprises the following steps: S1, synthetic hydrophilic polyester; S2. Synthesis of double-terminal epoxy silicone oil: Add terminal hydrogen silicone oil, allyl glycidyl ether and chloroplatinic acid catalyst into the reaction kettle, raise the temperature to 40-60°C, and keep warm for 5.5-6.5h; S3, adding the hydrophilic polyester described in step S1 and the double-terminal epoxy silicone oil described in step S2 into a reaction kettle at a molar ratio of (1-1.05):2, heating to 60-80° C., and keeping the temperature for 3.5-4.5 hours to obtain a polyester-polysiloxane copolymer; S4, adding a chain extender, wherein the molar ratio of the chain extender to the double-terminal epoxy silicone oil is 1:(1-1.05), and after the chain extension is completed, removing the solvent to obtain a quaternary amino-polyester-polysiloxane terpolymer; The chain extender is selected from tetramethylethylenediamine or tetramethylhexamethylenediamine; The hydrophilic polyester is selected from one of hydrophilic polyester A and hydrophilic polyester B; the hydrophilic polyester A is obtained by polymerizing lactic acid and polyethylene glycol; the hydrophilic polyester B is obtained by polymerizing succinic acid, 1,4-butanediol and polyethylene glycol.

4. The cotton feeling finishing agent according to claim 3, characterized in that The molar ratio of the terminal hydrogen-containing silicone oil to allyl glycidyl ether in step S2 is 1:(2.0-2.05); The amount of the catalyst chloroplatinic acid used in step S2 is 0.0001-0.0005% of the sum of the weight of the terminal hydrogen-containing silicone oil and allyl glycidyl ether; The temperature of adding the chain extender in step S4 is maintained at 80-85° C., and the temperature is kept for 2.8-3.2 hours after the chain extender is added. The adding method in step S4 is dropwise addition, and the dropwise addition time is 0.8-1.2 hours; The solvent removal in step S4 is as follows: adding an isoparaffin solvent for extraction and separation, and then transferring the mixture to a reaction kettle to remove the isoparaffin solvent by vacuum distillation.

5. The cotton feeling finishing agent according to claim 3, characterized in that: The preparation method of the hydrophilic polyester A comprises the following steps: A1. Add 1.0-1.05 parts of lactic acid and 1.0-1.05 parts of ionic liquid catalyst to the reactor by mass fraction, stir, introduce nitrogen, replace oxygen for 14-16 minutes, heat to 175-180°C, and keep warm for 0.4-0.6 hours; A2, adding 1.5-1.58 parts of polyethylene glycol by mass fraction, evacuating, heating from 175-180°C to 200-210°C, and keeping the temperature for 3.0-3.5 hours to obtain hydrophilic polyester A; The preparation method of the hydrophilic polyester B comprises the following steps: B1. Add 130-131 parts of succinic acid, 90-91 parts of 1,4-butanediol, and 120-121 parts of ionic liquid catalyst to the reactor by mass fraction, stir, introduce nitrogen, replace oxygen for 14-16 minutes, heat to 175-180°C, and keep warm for 0.4-0.6 hours; B2. If the degree of polymerization is qualified after sampling and detection, polyethylene glycol PEG2000 is added, and the mass ratio of polyethylene glycol to succinic acid is (1.52-1.53):

1. Vacuum the mixture, heat the mixture from 175-180°C to 200-210°C, and keep the temperature for 3.0-3.5 hours to obtain hydrophilic polyester B.

6. The cotton feeling finishing agent according to claim 5, characterized in that: The polyethylene glycol is selected from one or a combination of PEG400, PEG600, PEG1000 and PEG2000.

7. The cotton feeling finishing agent according to claim 5, characterized in that: The ionic liquid catalyst is [BMIM]CL-BiCL3.

8. The cotton feeling finishing agent according to claim 7, characterized in that: The preparation method of the ionic liquid catalyst comprises the following steps: C1, add 82.0-82.1 parts of 1-methylimidazole, 96-97 parts of 1-chloro-n-butane, and 49-50 parts of toluene into a reaction kettle, and react at 60-100° C. to obtain chloro-1-butyl-3-methylimidazole; C2. Under nitrogen protection, 312-315 parts of bismuth trichloride were added dropwise for 1.8-2.2 hours; the temperature was lowered during the period and controlled at 30-40° C. to obtain the ionic liquid catalyst [BMIM]CL-BiCL3.

9. The cotton feeling finishing agent according to claim 1, characterized in that: The emulsifier is selected from isomeric tridecanol polyoxyethylene ether 1307; and the solvent is selected from ethylene glycol butyl ether.

10. A method for preparing the cotton feeling finishing agent according to any one of claims 1 to 9, characterized in that: The method comprises the following steps: adding an emulsifier, a solvent and deionized water into a quaternary amino-polyester-polysiloxane terpolymer, mixing the mixture evenly and filtering the mixture to obtain the product.